Novel herbicides

ABSTRACT

Compounds of formula (I) wherein the substituents are as defined in claim  1 , and the agrochemically acceptable salts and all stereoisomeric and tautomeric forms of compounds of formula (I) are suitable for use as herbicides.

The present invention relates to novel, herbicidally active nicotinoyl derivatives, to processes for their preparation, to compositions comprising such compounds, and to their use in the control of weeds, especially in crops of useful plants, or in the inhibition of plant growth.

Nicotinoyl derivatives having herbicidal action are described, for example, in WO 00/15615, WO 00/39094 and WO 01/94339. Novel nicotinoyl derivatives having herbicidal and growth-inhibiting properties have now been found.

The present invention accordingly relates to compounds of formula I

wherein

-   L is either a direct bond, an —O—, —S—, —S(O)—, —SO₂—, —N(R_(5a))—,     —SO₂N(R_(5b))—, —N(R_(5b))SO₂—, —C(O)N(R_(5c))— or —N(R_(5c))C(O)—     bridge, or a C₁-C₄alkylene, C₂-C₄alkenylene or C₂-C₄alkynylene chain     which may be mono- or poly-substituted by R₅ and/or interrupted once     or twice by an —O—, —S—, —S(O)—, —SO₂—, —N(R_(5d))—, —SO₂N(R_(5e))—,     —N(R_(5e))SO₂—, —C(O)N(R_(5f))— and/or —N(R_(5f))C(O)— bridge, and     when two such bridges are present those bridges are separated at     least by one carbon atom, and W is bonded to L by way of a carbon     atom or a —N(R_(5e))SO₂— or —N(R_(5f))C(O)— bridge when the bridge L     is bonded to the nitrogen atom of W; -   W is a 4- to 7-membered, saturated, partially saturated or     unsaturated ring system U     which contains a ring element U₁, and may contain from one to four     further ring nitrogen atoms, and/or two further ring oxygen atoms,     and/or two further ring sulfur atoms and/or one or two further ring     elements U₂, and the ring system U may be mono- or poly-substituted     at a saturated or unsaturated ring carbon atom and/or at a ring     nitrogen atom by a group R₈, and two substituents R₈ together are a     further fused-on or spirocyclic 3- to 7-membered ring system which     may be unsaturated, partially saturated or fully saturated and may     in turn be substituted by one or more groups R_(8a) and/or     interrupted once or twice by a ring element —O—, —S—, —N(R_(8b))—     and/or —C(═O)—; and -   U₁ and U₂ are each independently of the other(s) —C(═O)—, —C(═S)—,     —C(═NR₆)—, —(N═O)—, —S(═O)— or —SO₂—; -   R₃ and R₄ are each independently of the other C₁-C₃alkyl,     C₁-C₃haloalkyl, C₁-C₃alkoxy-C₁-C₃alkyl, hydrogen, hydroxy, mercapto,     halogen, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkoxy-C₁-C₃alkoxy,     C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl,     C₁-C₃halo-alkylthio, C₁-C₃haloalkylsulfinyl, C₁-C₃haloalkylsulfonyl     or C₁-C₃alkylsulfonyloxy; -   R₅ is halogen, C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₃alkylthio,     C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, C₁-C₃alkoxy-C₁-C₃alkyl or     C₁-C₃alkoxy-C₁-C₃alkoxy; -   R_(5a), R_(5b) and R_(5e) are independently hydrogen, C₁-C₆alkyl,     C₃-C₆alkenyl, C₃-C₆alkynyl or C₁-C₃alkoxy-C₁-C₃alkyl; -   R_(5d) is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl,     C₁-C₃alkoxy-C₁-C₃alkyl, benzyl, cyano, formyl, C₁-C₄alkylcarbonyl,     C₁-C₄alkoxycarbonyl, C₁-C₄alkylsulfonyl or phenylsulfonyl, it being     possible for the phenyl-containing groups to be substituted by R₇; -   R_(5c) and R_(5f) are each independently of the other hydrogen or     C₁-C₃alkyl; -   R₆ is C₁-C₆alkyl, hydroxy, C₁-C₆alkoxy, cyano or nitro; -   R₇ is halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, hydroxy, C₁-C₃alkoxy,     C₁-C₃haloalkoxy, cyano or nitro; -   each R₈ independently is hydrogen, halogen, C₁-C₆alkyl,     C₁-C₆haloalkyl, C₃-C₆cycloalkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,     hydroxy, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy,     C₃-C₆alkynyloxy, C₁-C₃alkoxy-C₁-C₃alkoxy, mercapto, C₁-C₆alkylthio,     C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆alkylsulfonyloxy,     C₁-C₆haloalkylsulfonyloxy, C₃-C₆alkenylthio, C₃-C₆alkynylthio,     amino, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, C₁-C₃alkoxy-C₁-C₃alkyl,     formyl, C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl, benzyloxycarbonyl,     C₁-C₄alkylthiocarbonyl, carboxy, cyano, carbamoyl, phenyl, benzyl,     heteroaryl or heterocyclyl, it being possible for the phenyl,     benzyl, heteroaryl and heterocyclyl groups to be mono- or     poly-substituted by R_(7a); -   each R_(7a) independently is halogen, C₁-C₃alkyl, C₁-C₃haloalkyl,     hydroxy, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano or nitro; -   each R_(7a) independently is halogen, C₁-C₆alkyl, C₁-C₆haloalkyl,     C₃-C₆cycloalkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, hydroxy, C₁-C₆alkoxy,     C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, mercapto,     C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl,     C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl, cyano or nitro; -   R_(8b) is hydrogen, C₁-C₃alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl,     C₁-C₃alkoxy-C₁-C₃alkyl or benzyl, it being possible for the phenyl     group to be substituted by R_(7b); -   R_(7b) is halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, hydroxy, C₁-C₃alkoxy,     C₁-C₃haloalkoxy, cyano or nitro; -   p is 0 or 1; -   r is 1, 2, 3, 4, 5 or 6; -   with the provisos that -   a) R₈ and R_(8a) as halogen or hydrogenmercapto cannot be bonded to     a nitrogen atom, -   b) U₁ as —C(═O)— or —C(═S)— does not form a tautomeric form with a     substituent R₈ as hydrogen when the radical W is bonded to the     pyridyl group by way of a C₁-C₄alkylene, C₂-C₄alkenylene or     C₂-C₄alkynylene chain L that is interrupted by —O—, —S—, —S(O)—,     —SO₂—, —N(R_(5d))—, —SO₂N(R_(5e))— or —N(R_(5e))SO₂—, -   c) U₁ as —C(═S)— does not form a tautomeric form with a substituent     R₈ as hydrogen when the radical W is bonded to the pyridyl group by     way of a —CH═CH— or —C≡C— bridge L or by way of a C₁-C₄alkylene     chain L that is interrupted by —O—, —S—, —S(O)—, —SO₂— or     —N(C₁-C₄alkyl)—, -   d) U₁ as —C(═S)— or —C(═NR₆)— wherein R₆ is C₁-C₆alkyl or     C₁-C₆alkoxy does not form a tautomeric form with a substituent R₈ as     hydrogen when the radical W is bonded to the pyridyl group directly     or by way of a C₁-C₄alkylene chain L; either -   Q is a group Q₁     wherein -   A₁ is C(R₁₁R₁₂) or NR₁₃; -   A₂ is C(R₁₄R₁₅)_(m), C(O), oxygen, NR₁₆ or S(O)_(q); -   A₃ is C(R₁₇R₁₈) or NR₁₉;     -   with the proviso that A₂ is other than S(O)_(q) when A₁ is NR₁₃         and/or A₃ is NR₁₉; -   X₁ is hydroxy, O⁻M⁺, wherein M⁺ is a metal cation or an ammonium     cation; halogen or S(O)_(n)R₉,     wherein -   m is 1 or 2; -   q, n and k are each independently of the others 0, 1 or 2; -   R₉ is C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₂-C₁₂alkynyl, C₃-C₁₂allenyl,     C₃-C₁₂cycloalkyl, C₅-C₁₂cyclo-alkenyl, R₁₀-C₁-C₁₂alkylene or     R₁₀-C₂-C₁₂alkenylene, wherein the alkylene or alkenylene chain may     be interrupted by —O—, —S(O)_(k)— and/or —C(O)— and/or mono- to     penta-substituted by R₂₀; or phenyl, which may be mono- to     penta-substituted by R_(7c); -   R_(7c) is halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, hydroxy, C₁-C₃alkoxy,     C₁-C₃haloalkoxy, cyano or nitro; -   R₁₀ is halogen, cyano, rhodano, hydroxy, C₁-C₆alkoxy,     C₂-C₆alkenyloxy, C₂-C₆alkynyloxy, C₁-C₆alkylthio,     C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₂-C₆alkenylthio,     C₂-C₆alkynylthio, C₁-C₆alkylsulfonyloxy, phenylsulfonyloxy,     C₁-C₆alkylcarbonyloxy, benzoyloxy, C₁-C₄alkoxy-carbonyloxy,     C₁-C₆alkylcarbonyl, C₁-C₄alkoxycarbonyl, benzoyl, aminocarbonyl,     C₁-C₄alkyl-aminocarbonyl, C₃-C₆cycloalkyl, phenyl, phenoxy,     phenylthio, phenylsulfinyl or phenyl-sulfonyl; it being possible for     the phenyl-containing groups in turn to be substituted by R_(7d); -   R_(7d) is halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, hydroxy, C₁-C₃alkoxy,     C₁-C₃haloalkoxy, cyano or nitro; -   R₂₀ is hydroxy, halogen, C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkylthio,     C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, cyano, carbamoyl, carboxy,     C₁-C₄alkoxycarbonyl or phenyl; it being possible for phenyl to be     substituted by R_(7e); -   R_(7e) is halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, hydroxy, C₁-C₃alkoxy,     C₁-C₃haloalkoxy, cyano or nitro; R₁₁ and R₁₇ are each independently     of the other hydrogen, C₁-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl,     C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,     C₁-C₄alkoxycarbonyl, hydroxy, C₁-C₄alkoxy, C₃-C₄alkenyloxy,     C₃-C₄alkynyloxy, hydroxy-C₁-C₄alkyl,     C₁-C₄alkyl-sulfonyloxy-C₁-C₄alkyl, halogen, cyano or nitro; -   or, when A₂ is C(R₁₄R₁₅)_(m), R₁₇ together with R₁₁ forms a direct     bond or a C₁-C₃alkylene bridge; -   R₁₂ and R₁₈ are each independently of the other hydrogen, C₁-C₄alkyl     or C₁-C₄alkylthio, C₁-C₄alkylsulfinyl or C₁-C₄alkylsulfonyl; -   or R₁₂ together with R₁₁, and/or R₁₈ together with R₁₇ form a     C₂-C₅alkylene chain which may be interrupted by —O—, —C(O)—, —O— and     —C(O)— or —S(O)_(t)—; -   R₁₃ and R₁₉ are each independently of the other hydrogen,     C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₄alkenyl, C₃-C₄alkynyl or     C₁-C₄alkoxy; -   R₁₄ is hydrogen, hydroxy, C₁-C₄alkyl, C₁-C₄haloalkyl,     C₁-C₃hydroxyalkyl, C₁-C₄alkoxy-C₁-C₃-alkyl,     C₁-C₄alkylthio-C₁-C₃alkyl, C₁-C₄alkylcarbonyloxy-C₁-C₃alkyl,     C₁-C₄alkylsulfonyloxy-C₁-C₃alkyl, tosyloxy-C₁-C₃alkyl,     di(C₁-C₄alkoxy)-C₁-C₃alkyl, C₁-C₄alkoxycarbonyl,     C₃-C₅-oxacycloalkyl, C₃-C₅thiacycloalkyl, C₃-C₄dioxacycloalkyl,     C₃-C₄dithiacycloalkyl, C₃-C₄oxa-thiacycloalkyl, formyl,     C₁-C₄alkoxyiminomethyl, carbamoyl, C₁-C₄alkylaminocarbonyl or     di-(C₁-C₄alkyl)aminocarbonyl; -   or R₁₄ together with R₁₁, R₁₂, R₁₃, R₁₅, R₁₇, R₁₈ or R₁₉ or, when m     is 2, also together with R₁₄ forms a direct bond or a C₁-C₄alkylene     bridge; -   R₁₅ is hydrogen, C₁-C₃alkyl or C₁-C₃haloalkyl; -   R₁₆ is hydrogen, C₁-C₃alkyl, C₀-C₃haloalkyl, C₁-C₄alkoxycarbonyl,     C₁-C₄alkylcarbonyl or N,N-di(C₁-C₄alkyl)aminocarbonyl; or -   Q is a group Q₂     wherein -   R₂₁ and R₂₂ are hydrogen or C₁-C₄alkyl; -   X₂ is hydroxy, O⁻M⁺, wherein M⁺ is an alkali metal cation or     ammonium cation; halogen, C₁-C₁₂alkylsulfonyloxy, C₁-C₁₂alkylthio,     C₁-C₁₂alkylsulfinyl, C₁-C₁₂alkylsulfonyl, C₁-C₁₂halo-alkylthio,     C₁-C₁₂haloalkylsulfinyl, C₁-C₁₂haloalkylsulfonyl,     C₁-C₆alkoxy-C₁-C₆alkylthio, C₁-C₆-alkoxy-C₁-C₆alkylsulfinyl,     C₁-C₆alkoxy-C₁-C₆alkylsulfonyl, C₃-C₁₂alkenylthio,     C₃-C₁₂alkenyl-sulfinyl, C₃-C₁₂alkenylsulfonyl, C₃-C₁₂alkynylthio,     C₃-C₁₂alkynylsulfinyl, C₃-C₁₂alkynylsulfonyl,     C₁-C₄alkoxycarbonyl-C₁-C₄alkylthio,     C₁-C₄alkoxycarbonyl-C₁-C₄alkylsulfinyl,     C₁-C₄alkoxy-carbonyl-C₁-C₄alkylsulfonyl, benzyloxy or     phenylcarbonylmethoxy; it being possible for the phenyl-containing     groups to be substituted by R_(7f); -   R_(7f) is halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, hydroxy, C₁-C₃alkoxy,     C₁-C₃haloalkoxy, cyano or nitro; or -   Q is a group Q₃     wherein -   R₃₁ is C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl or     halo-substituted C₃-C₆cycloalkyl; -   R₃₂ is hydrogen, C₁-C₄alkoxycarbonyl, carboxy or a group S(O)₅R₃₃; -   R₃₃ is C₁-C₆alkyl or C₁-C₃alkylene, which may be substituted by     halogen, C₁-C₃alkoxy, C₂-C₃alkenyl or by C₂-C₃alkynyl; and -   s is 0, 1 or 2; or -   Q is a group Q₄     wherein -   R₄₁ is C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl or     halo-substituted C₃-C₆cycloalkyl; and to the agrochemically     acceptable salts and to all stereoisomers and tautomers of compounds     of formula I.

The alkyl groups appearing in the substituent definitions may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl and the branched isomers thereof. Alkoxy, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals. The alkenyl and alkynyl groups may be mono- or poly-unsaturated, C₂-C₁₁alkyl chains having one or more double or triple bonds also being included. Alkenyl is, for example, vinyl, allyl, isobuten-3-yl, CH₂═CH—CH₂—CH═CH₂—, CH₂═CH—CH₂—CH₂—CH═CH₂— or CH₃—CH═CH—CH₂CH═CH—. A preferred alkynyl is, for example, propargyl, and CH₂═C═CH₂— is a preferred allenyl.

An alkylene chain may be substituted by one or more C₁-C₃alkyl groups, especially by methyl groups; such alkylene chains and alkylene groups are preferably unsubstituted. The same applies to all groups containing C₃-C₆cycloalkyl, C₃-C₄oxacycloalkyl, C₃-C₅thiacycloalkyl, C₃-C₄dioxacycloalkyl, C₃-C₄dithiacycloalkyl or C₃-C₄oxaathiacycloalkyl.

An alkylene chain uninterrupted or interrupted by oxygen, S(O)_(k), —S(O)_(l), —NR₅— or by carbonyl and especially a C₁-C₄alkylene chain L which can be unsubstituted or substituted one or more times (up to five times) by R₅ and/or uninterrupted or interrupted once or twice by —O—, —S(O)_(l)—, —N(R_(5d))—, —SO₂N(R_(5e))—, —N(R_(5e))SO₂—, —C(O)N(R_(5f))— or —N(R_(5f))C(O)—, the latter being separated at least by one carbon atom, and W is bonded to L by way of a carbon atom or a —N(R_(5e))SO₂— or —N(R_(5f))C(O)— bridge when the bridge L is bonded to the nitrogen atom of W; is to be understood as being, for example, a chain —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂—, —CH(CH₃)—, —CH₂CH(CH₃)—, —CH₂CH(CH₃)CH₂—, —CH₂CH(Cl)CH₂—, —CH₂CH(OCH₃)CH₂—, —CH₂O—, —OCH₂—, —CH₂OCH₂—, —OCH₂CH₂—, —OCH₂CH₂CH₂—, —CH₂OCH₂CH₂—, —CH₂OCH(CH₃)CH₂—, —SCH₂—, —SCH₂CH₂—, —SCH₂CH₂CH₂—, —CH₂S—, —CH₂SCH₂—, —CH₂S(O)CH₂—, —CH₂SO₂CH₂—, —CH₂SCH₂CH₂—, —CH₂S(O)CH₂CH₂—, —CH₂SO₂CH₂CH₂—, —CH₂SO₂NH—, —CH₂N(CH₃)SO₂CH₂CH₂—, —N(SO₂Me)CH₂CH₂—, —CH₂C(O)NH— or —CH₂NHC(O)CH₂—. The definition R₁₀—C₁-C₁₂alkylene which may be interrupted by oxygen or by —S(O)_(n)— denotes, for example, CH₃OCH₂CH₂O—, phenoxy, phenoxymethyl, benzyloxy, benzylthio or benzyloxymethyl.

A C₂-C₄alkenylene chain which can be uninterrupted or interrupted by oxygen is accordingly to be understood as being, for example, —CH═CH—CH₂—, —CH═CH—CH₂CH₂— or —CH═CHCH₂OCH₂—, and a C₂-C₄alkynylene chain which can be uninterrupted or interrupted by oxygen is to be understood as being, for example, —C≡C—, —C≡CCH₂—, —C≡CCH₂O—, —C≡CCH₂OCH₂— or —OC≡CCH₂—.

An alkylene chain which can be mono- or poly-substituted by R₅ in C₁-C₄alkylene or by R₂₀ in R₁₀—C₁-C₁₂alkylene can be substituted, for example, up to five times. Two such substituents as C₁-C₃alkyl can together also form a 3- to 8-membered ring, the groups in question being located at the same carbon atom or at adjacent atoms.

W as a 4- to 7-membered, saturated, partially saturated or unsaturated ring system U

is to be understood as being especially a heterocyclic ring system U which contains a ring element U₁ and which may contain from one to four further ring nitrogen atoms, and/or one or two further ring oxygen atoms, and/or one or two further ring sulfur atoms and/or one or two further ring elements U₂, and which may be substituted one or more times (e.g. up to six times) at a saturated or unsaturated ring carbon atom and/or at a ring nitrogen atom by a group R₈, and in which two radicals R₈ together may be a further fused-on or spirocyclic 3- to 7-membered ring system, which may likewise be unsaturated, partially saturated or fully saturated and may itself be substituted by one or more groups R_(8a); and wherein U₁ and U₂ are each independently of the other —C(═O)—, —C(═S)—, —C(═NR₆)—, —(N═O)—, —S(═O)— or —SO₂—. Such ring systems U are, for example,

wherein R₅₄, R₅₆, R₅₈, R₅₉, R₆₂, R₆₃, R₆₆, R₆₇, R₆₈ and R₆₉ as sub-groups of selected substituents R₈ have the definitions and preferred meanings indicated hereinbelow.

Preferably W as a 4- to 7-membered, saturated, partially saturated or unsaturated ring system U is a heterocyclic group U₀

wherein R₁ together with R₂, by way of the nitrogen atom and the ring element U₁, forms the corresponding ring system U, which may additionally contain up to 3 nitrogen atoms, a further oxygen atom, a further sulfur atom or a further group U₂ and which may additionally be substituted one or more times (for example up to six times) at a saturated or unsaturated ring carbon atom and/or at a ring nitrogen atom by a group R₈, and in which two substituents R₈ together may be a further fused-on or spirocyclic 3- to 7-membered ring system, which may likewise be unsaturated, partially saturated or unsaturated and may itself be substituted by one or more groups R_(8a). W is especially a heterocycle selected from the groups

wherein R₅₁, R₅₃, R₅₆, R₆₅ are each independently of the others hydrogen, halogen, C₁-C₆-alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₃alkoxy-C₁-C₃alkyl, C₁-C₆alkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkyl-sulfonyl, C₃-C₆alkenylthio or C₃-C₆alkynylthio; R₅₂ is hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy, amino, or phenyl which may in turn be substituted by R₇₀; R₅₄, R₅₅, R₆₀ are hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl or C₃-C₆cycloalkyl; R₅₇, R₆₃, R₆₆, R₆₇, R₆₈, R₆₉ are C₁-C₆alkyl, or phenyl which may in turn be substituted by R₇₀; R₆₄ is C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl, C₃-C₆-alkenyl, C₃-C₆alkynyl, or phenyl which may in turn be substituted by R₇₀; R₅₈, R₆, are hydrogen, halogen, C₁-C₆alkyl or C₁-C₆haloalkyl; R₅₉ is C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₃-alkoxy-C₁-C₃alkyl, C₃-C₆alkenyl or C₃-C₆alkynyl; R₆₂ is hydrogen, C₁-C₆alkyl, C₁-C₄alkoxy-carbonyl or C₁-C₄alkylthiocarbonyl; or R₅₁ together with R₅₂, or R₅₄ together with an adjacent group R₅₆, or R₅₈ together with an adjacent group R₅₉, or R₆₀ together with an adjacent group R₆₁, or, when r is 2, two adjacent groups R₅₆ or two adjacent groups R₆₁ together may form a saturated or unsaturated C₁-C₅alkylene or C₃-C₄alkenylene bridge which may in turn be substituted by a group R₇₀ or interrupted by oxygen, sulfur or nitrogen; each R₇₀ independently is halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, hydroxy, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano or nitro; X is oxygen, sulfur or NR₆; X₃, X₄ and X₅ are oxygen or sulfur; X₆ and X₇ are oxygen or S, S(O), SO₂; and X₈ is CH₂, oxygen, S, S(O), SO₂ or NR₇₁, wherein R₇₁ is hydrogen or C₁-C₆alkyl.

Two substituents R₈ as hydroxy may be a further carbonyl group when they are located at the same carbon atom, and two substituents R₅ that together form a further 3- to 7-membered ring system can be located at the same carbon atom to form a spiro ring or at two adjacent carbon and/or nitrogen atoms to form a fused ring system, such as, for example, in the case of the groups:

The provisos that U₁ as either —C(═O)— or —C(═S)— or —C(═NR_(5d))— does not form a tautomeric form with a substituent R₈ as hydrogen are to be understood as meaning especially that an enol form is not formed under physiological conditions in a pH range of from about 2 to about 11. Accordingly, the present invention likewise relates, for example, to compounds of formulae

Halogen is generally fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine. The same is true of halogen in conjunction with other meanings, such as haloalkyl, haloalkoxy or halophenyl.

Haloalkyl groups having a chain length of from 1 to 6 carbon atoms are, for example, fluoro-methyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 1-fluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-fluoroprop-2-yl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, pentafluoro-ethyl, heptafluoro-n-propyl, perfluoro-n-hexyl. Preferred haloalkyl groups in the definitions R to R_(x), and particularly the group R₃, are fluoromethyl, difluoromethyl, difluorochloromethyl, trifluoromethyl and pentafluoroethyl.

As haloalkenyl there come into consideration alkenyl groups mono- or poly-substituted by halogen, halogen being fluorine, chlorine, bromine or iodine, and especially fluorine or chlorine, for example 1-chlorovinyl, 2-chlorovinyl, 2,2-difluoro-vinyl, 2,2-difluoro-prop-1-en-2-yl, 2,2-dichloro-vinyl, 3-fluoroprop-1-enyl, chloroprop-1-en-1-yl, 3-bromoprop-1-en-1-yl, 3-iodoprop-1-en-1-yl, 2,3,3-trifluoroprop-2-en-1-yl, 2,3,3-trichloroprop-2-en-1-yl and 4,4,4-trifluoro-but-2-en-1-yl.

As haloalkynyl there come into consideration, for example, alkynyl groups mono- or poly-substituted by halogen, halogen being bromine, iodine and especially fluorine or chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4trifluoro-but-2-yn-1-yl.

A C₃-C₆cycloalkyl group may likewise be mono- or poly-substituted by halogen, for example 2,2-dichlorocyclopropyl, 2,2-dibromocyclopropyl, 2,2,3,3-tetrafluorocyclobutyl or 2,2-difluoro-3,3-dichlorocyclobutyl.

Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy or a pentyloxy or hexyloxy isomer; preferably methoxy or ethoxy.

Haloalkoxy groups preferably have a chain length of from 1 to 6 carbon atoms, e.g. fluoro-methoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably fluoromethoxy, difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

Alkylthio groups preferably have a chain length of from 1 to 8 carbon atoms.

Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutyl-thio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutyl-sulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl or ethylsulfinyl.

Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methyl-sulfonyl or ethylsulfonyl.

Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or a butylamine isomer. Dialkylamino is, for example, dimethylamino, methylethylamino, diethyl-amino, n-propylmethylamino, dibutylamino or diisopropylamino. Alkylamino groups having a chain length of from 1 to 4 carbon atoms are preferred.

Alkoxyalkyl groups preferably have from 2 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl. Alkoxy-alkoxyalkyl groups preferably have from 3 to 8 carbon atoms, e.g. methoxymethoxymethyl, methoxyethoxymethyl, ethoxymethoxymethyl, ethoxyethoxymethyl. Di(C₁-C₄alkoxy)-C₁-C₄alkyl is to be understood as being, for example, dimethoxymethyl or diethoxymethyl.

Alkylthioalkyl groups preferably have from 2 to 6 carbon atoms. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl.

Alkylcarbonyl is preferably acetyl or propionyl. Alkoxycarbonyl is, for example, methoxy-carbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, iso-butoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl, ethoxycarbonyl or tert-butoxycarbonyl.

Phenyl, including as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl or tosyl, can be in mono- or poly-substituted form. The substituents can in that case be as desired, preferably with a substituent having a meaning of R₇ in the ortho-, meta- and/or para-position.

Heteroaryl is to be understood as being a 5- or 6-membered group containing both nitrogen and oxygen and/or sulfur, for example furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, thiazolyl, pyridyl, pyrimidinyl, triazinyl, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, 4,5-dihydro-isoxazole, 2-pyranyl, 1,3-dioxol-2-yl, oxiranyl, 3-oxetanyl, tetrahydrofuranyl, tetrahydropyranyl or one of the groups U₁ defined above.

Heterocyclyl is to be understood as being a ring system containing, in addition to carbon atoms, at least one hetero atom, such as nitrogen, oxygen and/or sulfur. It can be saturated or unsaturated. Heterocyclyl ring systems in the context of the present invention can also be substituted. Suitable substituents are, for example, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, cyano, nitro, C₁-C₄alkylsulfonyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylthio and C₃-C₆cycloalkyl.

The present invention relates also to the salts which the compounds of formula I and especially the compounds of formula Ia are able to form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal and alkaline earth metal bases as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially the hydroxides of sodium and potassium. Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C₁-C₁₋₈alkylamines, C₁-C₄hydroxyalkyl-amines and C₂-C₄alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexyl-amine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diiso-amylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, iso-propanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allyl-amine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propyl-amine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amyl-amine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine. Quaternary ammonium bases suitable for salt formation are, for example, [N(R_(a) R_(b) R_(c) R_(d))]⁺OH⁻ wherein R_(a), R_(b), R_(c) and R_(d) are each independently of the others C₁-C₄alkyl. Further suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions. M⁺ is preferably an ammonium salt, especially NH₄ ⁺, or an alkali metal, especially potassium or sodium.

Depending upon the preparation process, the compounds of formula I may be obtained in various tautomeric forms, such as, for example, in Form A shown below or in Form B or in Form C, preference being given to Form A, as shown by way of example for compounds of formula IA wherein Q is a group Q₁ and the group -L-W is in the 2-position.

When X₁ is hydroxy, the structure of formula I can also be represented by the tautomeric Form D

as shown likewise by way of the example of compounds of formula IA wherein Q is a group Q₁ and the group -L-W is in the 2-position. Compounds of formula I wherein Q is a group Q₂ or a group Q₄can accordingly be present in the tautomeric forms A, B, C or D. When a C═N or C═C double bond is present in compounds of formula I, the compounds of formula I, when asymmetric, may be in the E form or the Z form. When a further asymmetric centre is present, for example an asymmetric carbon atom, chiral R or S forms may occur. The present invention therefore relates also to all such stereoisomeric and tautomeric forms of the compound of formula I.

Of the compounds of formula I, the formulae IA, IB, IC, ID, IE, IF, IG and IH are preferred.

Special preference is given to the compounds of formula IA.

Of the compounds of formula I, special preference is given to those wherein W, as a 4- to 7-membered, saturated, partially saturated or unsaturated ring system U

is a group bonded to L by way of the nitrogen atom adjacent to the ring element U₁ and is accordingly a cyclic group U₀ mono- or poly-substituted by R₈

wherein R₁ together with R₂, by way of the nitrogen atom and the group U₁, forms the corresponding ring system U and wherein U₁, R₈ and r are as defined above.

Of the compounds of formula I and especially of the compounds of formula IA, special preference is given in turn to those groups wherein:

-   a) Q is a group Q₁, A₁ is CR₁₁R₁₂ and R₁₁ is hydrogen, methyl,     ethyl, propargyl, methoxy-carbonyl, ethoxycarbonyl, methylthio,     methylsulfinyl or methylsulfonyl and R₁₂ is hydrogen or methyl, or     R₁₁ together with R₁₂ forms an ethylene bridge —(CH₂)₂—; -   b) Q is a group Q₁ and A₂ is CR₁₄R₁₅ or an ethylene bridge —(CH₂)₂—,     and R₁₄ is hydrogen, methyl or trifluoromethyl and R₁₅ is hydrogen     or methyl, or R₁₄ together with R₁₁, or R₁₄ together with R₁₇ forms     a direct bond or a methylene bridge; -   c) Q is a group Q₁ and A₂ is C(O) and R₁₁, R₁₂, R₁₇ and R₁₈ are each     methyl; -   d) Q is a group Q₁ and A₂ is oxygen and R₁₁, R₁₂, R₁₇ and R₁₈ are     each hydrogen or methyl; -   e) Q is a group Q, and A₃ is CR₁₇R₁₈ and R₁₇ and R₁₈ are hydrogen or     methyl, or R₁₇ together with R₁, forms a methylene or ethylene     bridge; -   f) Q is a group Q, and X₁ is hydroxy; -   g) Q is a group Q₂ and R₂₁ is methyl or ethyl and R₂₂ is hydrogen or     methyl; -   h) Q is a group Q₂ and X₂ is hydroxy; -   i) Q is a group Q₃ or Q₄ and R₃₂ is hydrogen, methylthio or     methylsulfinyl, and R₃₁ and R₄₁ are cyclopropyl; -   j) p is 0; -   k) R₄ is hydrogen, methyl, chlorine or trifluoromethyl, especially     hydrogen; -   l) R₃ is C₁-C₃haloalkyl, especially difluoromethyl,     chlorodifluoromethyl or trifluoromethyl; -   m) L is either a direct bond or an unsubstituted C₁-C₃alkylene group     or a C₁-C₃alkylene group uninterrupted or interrupted by oxygen,     such as especially a methylene group —CH₂— or an     ethylenemethoxymethylene group —CH₂OCH₂CH₂—; -   n) R₁ and R₂ in the group —N(R₂)U₁R₁ form a 4- to 6-membered,     saturated or partially saturated ring system which may additionally     be substituted from one to three times by —N(R_(8b))—, once by     oxygen, once by sulfur, sulfinyl or sulfonyl and/or once by a     further carbonyl group; -   o) U₁ is preferably a —C(═O)— group, a —C(═S)— group, a C(═NR₆)—     group or a —SO₂— group; -   p) the group —N(R₂)U₁R₁ is -   q) the group —N(R₂)U₁R₁ is -   r) the group —N(R₂)U₁R₁ is -   s) the group —N(R₂)U₁R₁ is -   t) the group —N(R₂)U₁R₁ is     -   u) the group —N(R₂)U₁R₁ is -   v) the group —N(R₂)U₁R₁ is -   w) the group —N(R₂)U₁R₁ is a group selected from -   x) the group —N(R₂)U₁R₁ is     wherein X₆ is oxygen or sulfur; -   y) the group —N(R₂)U₁R₁ is     wherein X₇ is oxygen or sulfur;     -   z) the group —N(R₂)U₁R₁ is         wherein X is oxygen or sulfur and X₈ is —CH₂—; -   aa) the group —N(R₂)U₁R₁ is -   bb) the group —N(R₂)U₁R₁ is -   cc) the group —N(R₂)U₁R₁ is -   dd) the group —N(R₂)U₁R₁ is -   ee) the group —N(R₂)U₁R₁ is

Special preference is given to the compounds of formula IA

wherein Q, L, U₁, R₁, R₂, R₈ and r are as defined above and R₃ is difluoromethyl, chlorodifluoromethyl or trifluoromethyl, R₄ is hydrogen and p is 0.

The compounds of formula I can be prepared by means of processes known per se, as described below using the example of compounds of formula IA

wherein W is a heterocyclic group U₀

or, simplified,

and wherein the group -L-N(R₂)U₁R₁ is located in the 2-position of the nicotinoyl group. In a preferred process, for example for the preparation of a compound of formula IA

wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and Q is a group Q₁, Q₂ or Q₄, a compound of formula IIA

wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and Y is chlorine or cyano, is reacted in the presence of a base with a keto compound of formula IIIa, IIIb or IIId

wherein A₁, A₂, A₃, R₂₁, R₂₂ and R₄₁, are as defined above, thus yielding the compound of formula IA directly in situ or yielding a compound of formula IVA

wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and Q₀ is accordingly the group Q linked to oxygen, which compound, especially when Y is chlorine, is then rearranged in the presence of an additional amount of cyanide ions, e.g. potassium cyanide, trimethylsilyl cyanide or acetone cyanohydrin, and in the presence of a base, e.g. triethylamine, to form a C-C-linked compound IA.

That process is illustrated by way of example with respect to compounds of formula IA wherein Q is a group Q₁, that is to say with respect to compounds of formula IAa, in Scheme 1.

In a variant of that process, for example for the preparation of a compound of formula IA

wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and Q is a group Q₁, Q₂ or Q₄, a compound of formula IIAd

wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and R₀ is hydroxy, is reacted with the aid of a coupling reagent, for example dicyclohexylcarbodiimide, (1-chloro-2-methyl-propenyl)-dimethylamine or 2-chloro-1-methylpyridinium iodide, in the presence of a base, e.g. triethylamine or Hünig base, with a keto compound of formula IIIa, IIIb or IIId, respectively,

wherein A₁, A₂, A₃, R₂₁, R₂₂ and R₄₁ are as defined above, optionally via an intermediate of an activated ester of formula IIAe

wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and the meaning of Ye depends upon the coupling reagent used, to form a compound of formula IVA

wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and Q₀ is accordingly the group Q linked to oxygen, and that compound is then, after isolation in a second reaction step or directly in situ, rearranged in the presence of a base, e.g. triethylamine, and a catalytic amount of cyanide ions, e.g. potassium cyanide or acetone cyanohydrin, or a catalytic amount of dimethylaminopyridine, to form a C-C-linked compound IA.

That process is illustrated by way of example with respect to compounds of formula IA wherein Q is a group Q., that is to say with respect to compounds of formula IAa, in Scheme 2.

In a further process for the preparation of compounds of formula IA, a compound of formula VA

wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and T is chlorine, bromine, iodine or trifluoromethanesulfonyloxy, is reacted under carbonylation conditions, as described, for example, in Tetrahedron Letters, 31, 2841, 1990 and in WO 02/16305, in the presence of noble metal catalysts and suitable phosphine ligands, e.g. Pd(PPh₃)₄ or Pd(PPh₃)₂Cl₂, and suitable bases, e.g. triethylamine, with a compound of formula II, for example of formula IIIa or IIIb

wherein A₁, A₂, A₃, R₂₁ and R₂₂ are as defined above, as illustrated in Scheme 3 for compounds of formula IAa wherein X₁ is hydroxy.

Compounds of formula IA

wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and Q is a group Q₃

that is to say compounds of formula IAc, can likewise be prepared analogously to known procedures (for example analogously to the procedures described in WO 00/15615, WO 00/39094 and WO 01/94339), for example as follows: when X₃ is oxygen and R₃₂ is a group S(O)_(n)R₃₃ wherein R₃₃ is as defined above, a compound of formula IIA

wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and Y is chlorine is converted in a Claisen condensation with a ketocarboxylic acid salt of formula XIV R₃₁C(O)CH₂COO⁻M⁺  (XIV) or with a trialkyl silyl ester of formula XIVa R₃₁C(O)CH₂COOSi(R′R″R′″)₃  (XIVa), wherein R₃₁ is as defined above and M⁺ is a metal salt cation, e.g. Li⁺ or K⁺, and R′, R″, R′″ are an alkyl group, e.g. methyl, into a compound of formula IIAa

wherein L, U₁, R¹, R₂, R₃, R₄ and p are as defined above and Ya is CH₂C(O)R₃₁, that compound is then treated in the presence of a base with carbon disulfide and an alkylating reagent of formula XV R₃₃Y₂  (XV), wherein R₃₃ is as defined for formula I and Y₂ is a leaving group, such as halogen or sulfonyloxy, and converted into a compound of formula IIAb

wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and Yb is a group Yb

and then the compound of formula IIAb is cyclised with hydroxylamine hydrochloride and optionally in a solvent and in the presence of a base, for example sodium acetate, to form isomeric compounds of formula IAc and/or IAe, and the latter are then, when n is 1 or 2, oxidised with an oxidising agent, e.g. with a peracid, such as meta-chloroperbenzoic acid (m-CPBA) or peracetic acid, to form corresponding sulfoxides (n=1) or sulfones (n=2) of formula IAc

wherein L, U₁, R₁, R₂, R₃, R₄, R₃₁, and p are as defined above and R₃₂ is a group S(O)_(n)R₃₃. That process is illustrated in Scheme 4.

Compounds of formula IAc

wherein L, U₁, R₁, R₂, R₃, R₄, R₃₁ and p are as defined above and R₃₂ is hydrogen, C₁-C₄-alkoxycarbonyl or carboxy, can likewise be prepared analogously to known procedures (e.g. analogously to the procedures described in WO 97/46530), for example as follows: a compound of formula IIAa

wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and Ya is CH₂C(O)R₃₁, is converted in the presence of a base with an ortho ester of formula XVI R₃₂C(OR″)₂Y₃  (XVI) or with a cyanic acid ester of formula XVII R′″OC(O)CN  (XVII), wherein R₃₂ is hydrogen, Y₃ is a leaving group, such as C₁-C₄alkoxy or di(C₁-C₄alkyl)amino, and R′ and R′″ are C₁-C₄alkoxy, into a compound of formula IIAc

wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and Yc is a group Yc

wherein R₃₁ is as defined above and R₃₂ is hydrogen or C₁-C₄alkoxycarbonyl and Y₃ is a leaving group, such as C₁-C₄alkoxy or di(C₁-C₄alkyl)amino, or hydroxy, and then the compound of formula IIAc is cyclised with hydroxylamine hydrochloride and optionally in a solvent and in the presence of a base, for example sodium acetate, to form isomeric compounds of formula IAc and/or IAe, and the latter are then, when R₃₂ is carboxyl or hydrogen, treated with a hydrolysing agent, e.g. with potassium hydroxide followed by a mineral acid, such as hydrochloric acid, to yield compounds of formula IAc

wherein L, U₁, R₁, R₂, R₃, R₄, R₃₁ and p are as defined above and R₃₂ is hydrogen, C₁-C₄-alkoxycarbonyl or carboxy. That process is illustrated in Scheme 5.

The isomeric compounds of formula IAc and IAe can be separated and purified, for example by means of column chromatography and a suitable eluant. In addition, compounds of formula IAe represent a sub-group of compounds of formula IA and accordingly the present invention relates likewise thereto.

Compounds of formula IA

wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and X, or X₂ in the group Q₀ or Q₂, as the case may be, is S(O)_(n)R₉ can likewise be prepared in accordance with known procedures by reacting a compound of formula IA wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and X₁ or X₂ in the group Q, or Q₂, respectively, is hydroxy, with a chlorinating agent, e.g. with oxalyl chloride, and then reacting the resulting compound of formula IA wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and X₁ or X₂ in the group Q₁ or Q₂, respectively, is chlorine, with a thio compound of formula VI HSR₉  (VI) or with a salt of formula VIa M⁺⁻SR₉  (VIa), wherein R₉ is as defined above, and optionally with an additional base, e.g. triethylamine, sodium hydride, sodium hydrogen carbonate or potassium carbonate, and for the preparation of a compound of formula IA wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and X₁ or X₂ in the group Q₁ or Q₂, respectively, is S(O)_(n)R₉ and n is 1 or 2, treating the resulting compound of formula IA wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and X₁ or X₂ in the group Q₁ or Q₂, respectively, is SR₉, with an oxidising agent, e.g. sodium perbromate, sodium iodate, peracetic acid or m-chloroperbenzoic acid. That process sequence is illustrated in Scheme 6 using the example of compounds of formula IAa as defined above.

The compounds of formula IA

wherein Q, L, U₁, R₁, R₂, R₃, R₄ and p are as defined above can also be prepared by reacting a compound of formula XIIA

wherein Q, L, R₃, R₄ and p are as defined above and Y₀ is a leaving group, such as chlorine, bromine, mesyloxy or tosyloxy, with a corresponding amine compound of formula VIII HN(R₂)U₁R₁  (VII) or with a salt of formula VIIIa M⁺⁻N(R₂)U₁R₁  (VIIIa) wherein R₁, R₂ and U₁ are as defined above and M⁺ is a metal cation, it being possible to add a base, such as potassium carbonate, sodium hydride, sodium hydroxide, lithium hexa-methyldisilazane or lithium diisopropylamide. That general process is illustrated in Scheme 7.

The compounds of formula IIA

wherein L, U₁, R₁, R₂, R₃, R₄ and p are as defined above and Y is chlorine or cyano can be prepared by known methods from compounds of formula IIA wherein Y is hydroxy, C₁-C₄-alkoxy, benzyloxy, phenoxy or allyloxy, that is to say from compounds of formula IIAd

wherein L, U₁, R₀, R₁, R₂, R₃, R₄ and p are as defined above.

Such compounds of formula IIAa can be prepared, for example, from compounds of formula VIIA

wherein L, R₀, R₃, R₄ and p are as defined above and Y₀ is a leaving group, such as chlorine, bromine, mesyloxy or tosyloxy, with a corresponding amino compound of formula VIII HN(R₂)U₁R₁  (VIII) or with a salt of formula VIIIa M⁺⁻N(R₂)U₁R₁ (VIIIa) wherein R₁, R₂ and U₁ are as defined above and M⁺ is a metal cation, it being possible to, add a base, such as potassium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, lithium hexamethyidisilazane or lithium diisopropylamide. That general process is illustrated in Scheme 8.

Compounds of formulae IIA and IIAa

wherein L, U₁, R₀, R₁, R₂, R₄ and p are as defined above and R₃ is C₁-C₃haloalkyl can also be prepared by reacting a compound of formula IX

wherein L, U₁, R₀, R₁ and R₂ are as defined above, with an enamine of formula X

wherein R₄ is as defined above and R₃ is C₁-C₃haloalkyl, yielding a corresponding compound of formula IIAd

wherein L, U₁, R₀, R₁, R₂ and R₄ are as defined above and R₃ is C₁-C₃haloalkyl and p is 0, and that compound is then reacted further by generally known reaction methods for the conversion of the group R₀—O into a meaning of Y and optionally oxidation of the pyridyl nitrogen atom to the pyridyl-N-oxide, thus yielding a corresponding compound as defined above for formula IIA. That process is illustrated in Scheme 9.

Compounds of formula IX can be prepared by reacting an acetoacetic acid ester of formula XI R₀OC(O)CH₂C(O)CH₂Y₀  (XI), wherein Y₀ is especially chlorine or bromine and R₀ is C₁-C₄alkoxy, with a corresponding amino compound of formula VIII. HN(R₂)U₁R₁  (VIII) or with a salt of formula VIIIa M⁺⁻N(R₂)U₁R₁  (VIIIa), wherein R₁, R₂ and U₁ are as defined above and M⁺ is a metal cation, the reaction advantageously being carried out in the presence of potassium carbonate, sodium hydride, sodium hydroxide, lithium hexamethyldisilazane or lithium diisopropylamide as acid-binding agent and base. That process is illustrated in Scheme 10.

The compounds of formulae IIA, IIAa, IIAb, IIAc, IIAd, IVA and VA are valuable intermediates in the preparation of compounds of formula IA wherein R₃ is C₁-C₃haloalkyl and accordingly the present invention relates also thereto.

Those intermediates according to the invention are represented by the formula II

wherein Y is chlorine, cyano, hydroxy, C₁-C₄alkoxy, benzyloxy, phenoxy, allyloxy, a group

or a group Q₀, wherein Q₀ is accordingly a group Q linked to oxygen and Q, L, U₁, R₁, R₂, R₃, R₄, R₃₁, R₃₂, R₃₃ and p are as defined above for formula I.

The compounds of formula VII and especially compounds of formula VIIA are either known or can be prepared analogously to the methods described in WO 00/15615, WO 00/39094 and WO 01/94339. The compounds of formula XII and especially of formula XIIA are likewise known from the patent specifications mentioned above or can be prepared in accordance with the processes described therein.

The compounds of formula III used as starting materials are known or can be prepared in accordance with generally described methods, e.g. as described in the references mentioned above. The compounds of formula VIII are either known or can be prepared analogously to known methods, e.g. according to WO 99/18089.

All other compounds of formula I, such as especially those of formulae IB, IC, ID, IE, IF, IG and IH, can be prepared analogously to the processes described above.

The reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents. Such solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetra-chloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as aceto nitrile or propionitrile, amides, such as N,N-dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are preferably from −20° C. to +120° C. If the reactions proceed slightly exothermically, they can generally be carried out at room temperature. In order to shorten the reaction time or to initiate the reaction, brief heating, up to the boiling point of the reaction mixture, can be carried out. The reaction times can likewise be shortened by the addition of suitable bases as reaction catalysts. As bases there are used especially the tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 2-methyl-4-ethylpyridine, dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo-[4.3.0]non-5-ene or 1,5-diazabicyclo[5.4.0]undec-7-ene. It is also possible, however, to use as bases inorganic bases, such as hydrides, e.g. sodium or calcium hydride, hydroxides, e.g. dry sodium or potassium hydroxide, carbonates, e.g. sodium or potassium carbonate, or hydrogen carbonates, e.g. sodium or potassium hydrogen carbonate.

According to Reaction Schemes 6, 8 and 9, the compounds of formulae I and II are prepared using a chlorinating agent, e.g. thionyl chloride, phosgene, phosphorus pentachloride, phosphorus oxychloride or preferably oxalyl chloride. The reaction is preferably carried out in an inert organic solvent, for example in aliphatic, halogenated aliphatic, aromatic or halogenated aromatic hydrocarbons, for example n-hexane, benzene, toluene, xylenes, dichloro-methane, 1,2-dichloroethane or chlorobenzene, at reaction temperatures in the range from −20° C. up to the reflux temperature of the reaction mixture, preferably at about from +40 to +100° C., and in the presence of a catalytic amount of N,N-dimethylformamide.

For the preparation of compounds of formulae I and IV according to Reaction Scheme 1 or with the aid of a coupling reagent, for example dicyclohexylcarbodiimide, (1-chloro-2-methyl-propenyl)-dimethylamine or 2-chloro-1-methylpyridinium iodide, according to Reaction Scheme 2, reaction is preferably likewise carried out in one of the inert organic solvents mentioned above at temperatures from about −20° C. to about +100° C., preferably from about +5° C. to about +50° C.

The end products of formula I can be isolated in conventional manner by concentration or evaporation of the solvent and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, by distillation or by means of column chromatography or by means of the HPLC technique using a suitable eluant.

The sequence in which the reactions should be carried out in order as far as possible to avoid secondary reactions will also be familiar to the person skilled in the art. Unless the synthesis is specifically aimed at the isolation of pure isomers, the product may be obtained in the form of a mixture of two or more isomers, for example chiral centres in the case of alkyl groups or cis/trans isomerism in the case of alkenyl groups or <E> or <Z> forms, e.g. in respect of a —C(═NR₆)— group. All such isomers can be separated by methods known per se, for example chromatography, crystallisation, or produced in the desired form by means of a specific reaction procedure.

Compounds of formula I wherein p is 1, that is to say the corresponding pyridyl-N-oxides of formula I, can be prepared by reacting a compound of formula I wherein p is 0 with a suitable oxidising agent, for example with the H₂O₂ urea adduct in the presence of an acid anhydride, e.g. the trifluoroacetic anhydride. That reaction can be carried out either with compounds of formula I or at the stage of compounds of formula II, V, VII or XII.

For the use according to the invention of the compounds of formula I, or of compositions comprising them, there come into consideration all methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques such as, for example, the controlled release of active ingredient. For that purpose a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If required, it is additionally possible to apply a coating (coated granules), which allows the active ingredient to be released in metered amounts over a specific period of time.

The compounds of formula I can be used as herbicides in unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, suspensions, mixtures of a suspension and an emulsion (suspoemulsions), wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are selected in accordance with the intended objectives and the prevailing circumstances.

The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers. Surface-active compounds (surfactants) may also be used in addition in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, on page 6 of WO 97/34485.

Depending upon the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.

Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485.

In addition, the surfactants conventionally employed in formulation technology, which are described, inter alia, in “McCutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood N.J., 1981, Stache, H., “Tensid-Taschenbuch”, Carl Hanser Verlag, Munich/Vienna 1981, and M. and J. Ash, “Encyclopedia of Surfactants”, Vol. I-III, Chemical Publishing Co., New York, 1980-81, are also suitable for the preparation of the herbicidal compositions according to the invention.

The compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters thereof or mixtures of such oils and oil derivatives.

The amounts of oil additive in the composition according to the invention is generally from 0.01 to 2%, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared.

Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® obtainable from Rhone-Poulenc Canada Inc., alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains as active components essentially 80% by weight alkyl esters of fish oils and 15% by weight methylated rapeseed oil, and also 5% by weight of customary emulsifiers and pH modifiers.

Especially preferred oil additives comprise alkyl esters of higher fatty acids (C₈-C₂₂), especially the methyl derivatives of C₁₂-C₁₈fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Henkel subsidiary Cognis GMBH, DE)

The application and action of the oil additives can be improved by combining them with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485.

Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C₁₂-C₂₂fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available, preferred surfactants are the Genapol types (Clariant A G, Muttenz, Switzerland). Also preferred for use as surface-active substances are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltrisiloxanes, such as are commercially available as e.g. Silwet L-77®, and also perfluorinated surfactants. The concentration of surface-active substances in relation to the total additive is generally from 1 to 30% by weight.

Examples of oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Zeneca Agro, Stoney Creek, Ontario, Calif.) and Actipron® (BP Oil UK Limited, GB).

The addition of an organic solvent to the oil additive/surfactant mixture can also bring about a further enhancement of action. Suitable solvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation) types. The concentration of such solvents can be from 10 to 80% by weight of the total weight.

Such oil additives, which are also described, for example, in U.S. Pat. No. 4,834,908, are suitable for the composition according to the invention. A commercially available oil additive is known by the name MERGE®, is obtainable from the BASF Corporation and is essentially described, for example, in U.S. Pat. No. 4,834,908 in col. 5, as Example COC-1. A further oil additive that is preferred according to the invention is SCORE® (Novartis Crop Protection Canada.)

In addition to the oil additives listed above, in order to enhance the action of the compositions according to the invention it is also possible for formulations of alkyl pyrrolidones, such as are commercially available e.g. as Agrimax®, to be added to the spray mixture. Formulations of synthetic latices, such as, for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene, such as are commercially available as e.g. Bond®, Courier® or Emerald®, can also be used to enhance action. Solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, can also be added as action-enhancing agent to the spray mixture.

The herbicidal formulations generally contain from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of herbicide, from 1 to 99.9% by weight, especially from 5 to 99.8% by weight, of a solid or liquid formulation adjuvant, and from 0 to 25% by weight, especially from 0.1 to 25% by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.

The compounds of formula I are generally applied to plants or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.

The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control.

The term ‘crops’ is to be understood as including also crops that have been rendered tolerant to herbicides or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. Imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.

The weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.

The following Examples further illustrate the invention but do not limit the invention.

PREPARATION EXAMPLE P1 2-[6-(Chloro-difluoro-methyl)-3-(2-hydroxy-6-oxo-cyclohex-1-ene-carbonyl)-pyridin-2-ylmethyl]-4-methyl-5-trifluoromethyl-2.4-dihydro-[1.2.4]triazol-3-one:

65 mg (0.17 mmol) of 6-(chloro-difluoro-methyl)-2-(4-methyl-5-oxo-3-trifluoromethyl-4,5-dihydro-[1.2.4]triazol-1-ylmethyl)-nicotinic acid (Preparation Example P6) are heated at 50° C. for 30 minutes in 5 ml of hexane with 0.02 ml of oxalyl chloride and a catalytic amount of dimethylformamide. The mixture is then concentrated by evaporation and taken up in 1 ml of acetonitrile, and the 6-(chloro-difluoro-methyl)-2-(4-methyl-5-oxo-3-trifluoromethyl-4,5-dihydro[1.2.4]triazol-1-ylmethyl)-nicotinic acid chloride so prepared is transferred into a solution of 60 mg (0.15 mmol) of cyclohexane-1,3-dione and 40 mg (0.4 mmol) of triethyl-amine in 2 ml of acetonitrile. After 40 minutes' stirring at room temperature, 1 drop of acetone cyanohydrin is added and stirring is continued for a further 2 hours. The reaction product is then taken up in ethyl acetate and washed once with dilute hydrochloric acid and once with sodium chloride solution, concentrated and purified by chromatography using the HPLC technique. Pure 2-[6-(chloro-difluoro-methyl)-3-(2-hydroxy-6-oxo-cyclohex-1-ene-carbonyl)-pyridin-2-ylmethyl]-4-methyl-5-trifluoromethyl-2,4-dihydro-[1.2.4]triazol-3-one is thus obtained in the form of a resin; ¹H-NMR (CDCl₃ in ppm relative to TMS): 16.96, b, 1H; 7.60, m, 2H, 5.18, s, 2H, 3.33, s, 3H, 2.82, m, 2H, 2.50, m, 2H, 2.19, m, 2H.

PREPARATION EXAMPLE P2 3-[3-(2-Hydroxy-6-oxo-cyclohex-1-enecarbonyl)-6-trifluoromethyl-pyridin-2-ylmethyl]-5-methyl-3H-[1.3.4]oxadiazol-2-one:

514 mg (1.694 mmol) of 2-(5-methyl-2-oxo-[1.3.4]oxadiazol-3-ylmethyl)-6-trifluoromethyl-nicotinic acid (Preparation Example P4) are introduced into 20 ml of dry methylene chloride. At 0° C., 0.264 ml (1.864 mmol) of (1-chloro-2-methyl-propenyl)-dimethyl-amine are squirted in and the mixture is then stirred at 20° C. for 2 hours. At 0° C., 0.190 g (1.694 mmol) of cyclo-hexane-1,3-dione and 0.354 ml (2.542 mmol) of triethylamine are then added and the mixture is stirred at 20° C. for 2 hours. The mixture is concentrated by evaporation and taken up in 20 ml of anhydrous acetonitrile, and 0.354 ml (2.542 mmol) of triethylamine and 0.155 ml (1.694 mmol) of acetone cyanohydrin are added to the reaction mixture. The reaction mixture is stirred at 20° C. for a further 20 hours and then concentrated by evaporation. The residue is purified by chromatography. The fractions are combined and concentrated. 0.570 g (84.7%) of pure 3-[3-(2-hydroxy-6-oxo-cyclohex-1-enecarbonyl)-6-trifluoromethyl-pyridin-2-ylmethyl]-5-methyl-3H-[1.3.4]oxadiazol-2-one is thus obtained in the form of a beige solid; ¹H-NMR (CDCl₃ in ppm relative to TMS): 17.6, b, 1H, 7.65, m, 2H, 4.98, s, 2H, 2.84, m, 2H, 2.48, m, 2H, 2.20, s, 3H, 2.08, m, 2H.

PREPARATION EXAMPLE P3 3-{2-[3-(2-Hydroxy-4-oxo-bicyclo[3.2.1]oct-2-ene-3-carbonyl)-6-trifluoromethyl-pyridin-2-ylmethoxy]-ethyl}-5-methyl-3H-[1.3.4]thiadiazol-2-one

71 mg (1.635 mmol) of sodium hydride in the form of a 55% dispersion in oil are introduced into 2 ml of dry DMF. At 0° C., a solution of 300 mg (0.743 mmol) of 3-[2-(2-chloro-ethoxy-methyl)-6-trifluoromethyl-pyridine-3-carbonyl]-4-hydroxy-bicyclo[3.2.1]oct-3-en-2-one in 4 ml of anhydrous DMF is added dropwise. The reaction mixture is stirred at room temperature for 2 hours. In parallel, a further 71 mg (1.635 mmol) of sodium hydride in the form of a 55% dispersion in oil are introduced into a second flask and, at 0° C., 95 mg (0.817 mmol) of 5-methyl-3H-[1.3.4]thiadiazol-2-one are added. This mixture is also stirred at room temperature for 2 hours. Then, at the same temperature, the contents of the second flask are rapidly added to the reaction mixture in the first flask. The combined reaction mixture is then stirred at 20° C. for 4 hours and at 80° C. for 16 hours. The reaction product is poured into water and extracted with ethyl acetate. The organic phases are washed once with sodium chloride solution, dried over sodium sulfate and concentrated. The residue is purified by chromatography. 200 mg (55.7%) of pure 3-{2-[3-(2-hydroxy-4-oxo-bicyclo[3.2.1]oct-2-ene-3-carbonyl)-6-trifluoromethyl-pyridin-2-ylmethoxy]-ethyl}-5-methyl-3H-[1.3.4]thiadiazol-2-one are thus obtained in the form of a resin; ¹H-NMR (CDCl₃ in ppm relative to TMS): 16.9, b, 1H; 7.6, m, 2H, 4.72, s, 2H, 3.87, t, 2H, 3.62, t, 2H, 3.15, m, 1H, 2.87, m, 1H, 2.35, s, 3H, 2.3-2.0, m, 4H, 1.75, m, 2H.

PREPARATION EXAMPLE P4 2-(5-Methyl-2-oxo-[1.3.4]oxadiazol-3-ylmethyl)-6-trifluoromethyl-nicotinic acid

500 mg (1.509 mmol) of 2-(5-methyl-2-oxo-[1.3.4]oxadiazol-3-ylmethyl)-6-trifluoromethyl-nicotinic acid ethyl ester (Preparation Example P5) are introduced into 40 ml of a 1:1 mixture of THF/water at room temperature. At 0° C., 69.7 mg (1.66 mmol) of LiOH.H₂O are added. The reaction mixture is then stirred at the same temperature for 30 minutes. The reaction product is then extracted with ethyl acetate, washed with saturated sodium chloride solution, dried over sodium sulfate and concentrated by evaporation, yielding 420 mg (92%) of 2-(5-methyl-2-oxo-[1.3.4]oxadiazol-3-ylmethyl)-6-trifluoromethyl-nicotinic acid in the form of a white solid; ¹H-NMR (CD₃CN in ppm relative to TMS): 8.55, d, 1H; −7.82, d, 1H, 5.39, s, 2H; 2.20, s, 3H.

PREPARATION EXAMPLE P5 2-(5-Methyl-2-oxo-[1.3.4]oxadiazol-3-ylmethyl)-6-trifluoromethyl-nicotinic acid ethyl ester

2.0 g (7.45 mmol) of 2-chloromethyl-6-trifluoromethyl-nicotinic acid ethyl ester are introduced into 8 ml of dry DMF at room temperature, and 1.0 g (8.19 mmol) of the sodium salt of 5-methyl-3H-[1.3.4]oxadiazol-2-one is added. The reaction mixture is then stirred at the same temperature for 20 hours. The reaction product is then diluted with water and extracted with ethyl acetate. The organic phases are washed once with sodium chloride solution, dried over sodium sulfate and concentrated. The residue is concentrated by evaporation and purified by chromatography, yielding 2.04 g (82%) of 2-(5-methyl-2-oxo-[1.3.4]oxadiazol-3-ylmethyl)-6-trifluoromethyl-nicotinic acid ethyl ester in the form of a white powder; ¹H-NMR (CDCl₃ in ppm relative to TMS): 8.48, d, 1H, 7.67, d, 1H, 5.45, s, 2H, 4.42, q, 2H, 2.26, s, 3H; 1;43, t, 3H.

PREPARATION EXAMPLE P6 2-(3-Methyl-imidazolidin-2-on-1-ylmethyl)-6-trifluoromethylnicotinic acid

1.66 g (16.6 mmol) of 1-methyl-2-imidazolidinone are introduced into 50 ml of dry tetra-hydrofuran. At room temperature, 0.96 g (16.6 mmol) of pulverulent potassium hydroxide and 0.15 g (0.55 mmol) of 1,4,7,10,13,16-hexaoxacyclooctadecane are added thereto. The reaction mixture is stirred at room temperature for 2.5 hours. Then 1.48 g (5.53 mmol) of 2-chloromethyl-6-trifluoromethylnicotinic acid ethyl ester in 10 ml of dry tetrahydrofuran are added dropwise at room temperature in the course of 20 minutes. The reaction mixture is stirred at the same temperature for 22 hours. The reaction product is then diluted with water and extracted with ethyl acetate. The organic phases are washed with water. The aqueous phases are combined and rendered acidic with HCl (1 M solution). The aqueous phase is then extracted with ethyl acetate and the organic phases from the acidic extraction are combined, dried over sodium sulfate and concentrated. The residue is concentrated by evaporation, diluted with 8 ml of tetrabutyl methyl ether (TBME), stirred, filtered, concentrated, and dried under a high vacuum. 1.09 g of 2-(3-methyl-imidazolidin-2-on-1-ylmethyl)-6-trifluoromethylnicotinic acid are obtained in the form of a light-beige solid; ¹H-NMR (CD₃OD in ppm relative to TMS): 8.52, d, 1H, 7.78, d, 1H, 4.94, s, 2H, 3.65-3.35, 2×m, 2×2H, 2.82, s, 3H.

PREPARATION EXAMPLE P7 6-(Chloro-difluoro-methyl)-2-(4-methyl-5-oxo-3-trifluoromethyl-4.5-dihydro-[1.2.4]triazol-1-ylmethyl)-nicotinic acid:

1 g (30 mmol) of 90% 4-(4-methyl-5-oxo-3-trifluoromethyl-4,5-dihydro-[1.2.4]triazol-1-yl)-3-oxo-butyric acid ethyl ester (Preparation Example P7) and 0.52 g (31 mmol) of 4-amino-1-chloro-1,1-difluoro-but-3-en-2-one are together heated at boiling temperature for 8 hours in 30 ml of toluene in the presence of 0.14 ml (1.8 mmol) of trifluoroacetic acid. The reaction product is then taken up in ethyl acetate and washed once with sodium hydrogen carbonate solution and once with sodium chloride solution. The residue is concentrated by evaporation and purified by chromatography, and 6-(chloro-difluoro-methyl)-2-(4-methyl-5-oxo-3-trifluoro-methyl-4,5-dihydro-[1.2.4]triazol-1-ylmethyl)-nicotinic acid ethyl ester is thus obtained in the form of an 80% product; ¹H-NMR (CDCl₃ in ppm relative to TMS): 8.45, d, 1H, 7.62, d, 1H; 5.65, s, 2H, 4.38, q, 2H, 3.45, s, 3H, 1.44, t, 3H.

The product is then hydrolysed in the presence of 1.4 equivalents of potassium hydroxide in a 1:1 mixture of dioxane/water at room temperature. The organic solvent and neutral secondary components are removed with diethyl ether and the aqueous phase is then acidified with hydrochloric acid and extracted with ethyl acetate. Pure 6-(chloro-difluoro-methyl)-2-(4-methyl-5-oxo-3-trifluoromethyl-4,5-dihydro-[1.2.4]triazol-1-ylmethyl)-nicotinic acid is thus obtained in the form of a crystalline product; ¹H-NMR (CDCl₃ in ppm relative to TMS): 10.42, b, 1H, 8.42, d, 1H, 7.61, d, 1H, 5.72, s, 2H, 3.50, s, 3H.

PREPARATION EXAMPLE P8 4-(4-Methyl-5-oxo-3-trifluoromethyl-4.5-dihydro-[1.2.4]triazol-1-yl)-3-oxo-butyric acid ethyl ester

1.35 g (31 mol) of sodium hydride in the form of a 55% dispersion in oil are introduced into 30 ml of tetrahydrofuran. 2.55 g (15 mmol) of solid 4-methyl-5-trifluoromethyl-2,4-dihydro-[1.2.4]triazol-3-one hydroiodide are stirred in at room temperature and the mixture is briefly heated to 40° C. to complete the evolution of hydrogen. 1.95 ml (13.8 mmol) of 4-chloro-acetoacetic acid ethyl ester are then added dropwise to the resulting viscous suspension at a temperature of 20° C.; 4 drops of 15-crown-5 are added and the mixture is stirred at the same temperature for 16 hours. The reaction product is then poured into water and adjusted to pH 3 with hydrochloric acid, extracted with diethyl ether, washed with saturated sodium chloride solution and concentrated by evaporation. The residue is purified by chromatography (ethyl acetate/hexane gradient), 4-(4-methyl-5-oxo-3-trifluoromethyl-4,5-dihydro-[1.2.4]triazol-1-yl)-3-oxo-butyric acid ethyl ester being obtained in the form of a viscous oil; ¹H-NMR (CDCl₃ in ppm relative to TMS): 4.83, s, 2H, 4.22, q, 2H, 3.55, s, 2H, 3.39, s, 3H; 1.28, t, 3H.

All further compounds of formula I can be prepared analogously to the preparation methods and Examples described above.

In the following Tables, the linkage site of the individual structures of the group

to the substituent L is the nitrogen atom located at the same geometric position, as indicated in each case.

For example, the linkage site of the group

in the case of compound A 1.001 is the position indicated by an arrow:

The free valencies in these structures are terminal CH₃ groups, such as, for example, in the case of the structure

which can also be represented as follows: N

TABLE A1 Compounds of formula IAa₁: (IAa₁)

Comp. No. R₃ L

Phys. data A1.001 (P1) CF₂Cl

resin A1.002 CF₂H CH₂

A1.003 CF₃ CH₂

A1.004 CF₃ CH₂OCH₂CH₂

A1.005 CF₂Cl CH₂OCH₂CH₂

A1.006 CHF₂ CH₂OCH₂CH₂

A1.007 CF₃ CH₂

solid A1.008 CF₂Cl CH₂

A1.009 CHF2 CH₂

A1.010 CF₃ CH₂OCH₂CH₂

A1.011 CF₂Cl CH₂OCH₂CH₂

A1.012 CHF₂ CH₂OCH₂CH₂

A1.013 CF₃ CH₂

A1.014 CF₂Cl CH₂

A1.015 CHF₂ CH₂

A1.016 CF₃ CH₂OCH₂CH₂

A1.017 CF₂Cl CH₂OCH₂CH₂

A1.018 CHF₂ CH₂OCH₂CH₂

A1.019 CF₃ CH₂

solid A1.020 CF₂Cl CH₂

A1.021 CHF₂ CH₂

A1.022 CF₃ CH₂OCH₂CH₂

A1.023 CF₂Cl CH₂OCH₂CH₂

A1.024 CHF₂ CH₂OCH₂CH₂

A1.025 CF₃ CH₂

solid A1.026 CF₂Cl CH₂

A1.027 CHF₂ CH₂

A1.028 CF₃ CH₂OCH₂CH₂

A1.029 CF₂Cl CH₂OCH₂CH₂

A1.030 CHF₂ CH₂OCH₂CH₂

A1.031 CF₃ CH₂

solid A1.032 CF₂Cl CH₂

A1.033 CHF₂ CH₂

A1.034 CF₃ CH₂OCH₂CH₂

A1.035 CF₂Cl CH₂OCH₂CH₂

A1.036 CHF₂ CH₂OCH₂CH₂

A1.037 CF₃ CH₂

solid A1.038 CF₂Cl CH₂

A1.039 CHF₂ CH₂

A1.040 CF₃ CH₂OCH₂CH₂

A1.041 CF₂Cl CH₂OCH₂CH₂

A1.042 CHF₂ CH₂OCH₂CH₂

A1.043 CF₃ CH₂

resin A1.044 CF₂Cl CH₂

A1.045 CHF₂ CH₂

A1.046 CF₃ CH₂OCH₂CH₂

A1.047 CF₂Cl CH₂OCH₂CH₂

A1.048 CHF₂ CH₂OCH₂CH₂

A1.049 CF₃ CH₂

resin A1.050 CF₂Cl CH₂

A1.051 CHF₂ CH₂

A1.052 CF₃ CH₂OCH₂CH₂

A1.053 CF₂Cl CH₂OCH₂CH₂

A1.054 CHF₂ CH₂OCH₂CH₂

A1.055 CF₃ CH₂

resin A1.056 CF₂Cl CH₂

A1.057 CHF₂ CH₂

A1.058 CF₃ CH₂OCH₂CH₂

A1.059 CF₂Cl CH₂OCH₂CH₂

A1.060 CHF₂ CH₂OCH₂CH₂

A1.061 CF₃ CH₂

A1.062 CF₂Cl CH₂

A1.063 CHF₂ CH₂

A1.064 CF₃ CH₂OCH₂CH₂

A1.065 CF₂Cl CH₂OCH₂CH₂

A1.066 CHF₂ CH₂OCH₂CH₂

A1.067 CF₃ CH₂

A1.068 CF₂Cl CH₂

A1.069 CHF₂ CH₂

A1.070 CF₃ CH₂OCH₂CH₂

A1.071 CF₂Cl CH₂OCH₂CH₂

A1.072 CHF₂ CH₂OCH₂CH₂

A1.073 CF₃ CH₂

m.p.: 140° C. A1.074 CF₂Cl CH₂

m.p.: 125-127° C. A1.075 CHF₂ CH₂

A1.076 CF₃ CH₂OCH₂CH₂

A1.077 CF₂Cl CH₂OCH₂CH₂

A1.078 CHF₂ CH₂OCH₂CH₂

A1.079 CF₃ CH₂

amorphous crystals A1.080 CF₂Cl CH₂

A1.081 CHF₂ CH₂

A1.082 CF₃ CH₂OCH₂CH₂

resin A1.083 CF₂Cl CH₂OCH₂CH₂

A1.084 CHF₂ CH₂OCH₂CH₂

A1.085 CF₃ CH₂

amorphous crystals A1.086 CF₂Cl CH₂

A1.087 CHF₂ CH₂

A1.088 CF₃ CH₂OCH₂CH₂

A1.089 CF₂Cl CH₂OCH₂CH₂

A1.090 CHF₂ CH₂OCH₂CH₂

A1.091 CF₃ CH₂

resin A1.092 CF₂Cl CH₂

A1.093 CHF₂ CH₂

A1.094 CF₃ CH₂OCH₂CH₂

A1.095 CF₂Cl CH₂OCH₂CH₂

A1.096 CHF₂ CH₂OCH₂CH₂

A1.097 (P2) CF₃ CH₂

amorphous crystals A1.098 CF₂Cl CH₂

m.p.: 130-132° C. A1.099 CHF₂ CH₂

A1.100 CF₃ CH₂OCH₂CH₂

resin A1.101 CF₂Cl CH₂OCH₂CH₂

A1.102 CHF₂ CH₂OCH₂CH₂

A1.103 CF₃ CH₂

resin A1.104 CF₂Cl CH₂

A1.105 CHF₂ CH₂

A1.106 CF₃ CH₂OCH₂CH₂

A1.107 CF₂Cl CH₂OCH₂CH₂

A1.108 CHF₂ CH₂OCH₂CH₂

A1.109 CF₃ CH₂

resin A1.110 CF₂Cl CH₂

A1.111 CHF₂ CH₂

A1.112 CF₃ CH₂OCH₂CH₂

A1.113 CF₂Cl CH₂OCH₂CH₂

A1.114 CHF₂ CH₂OCH₂CH₂

A1.115 CF₃ CH₂

resin A1.116 CF₂Cl CH₂

A1.117 CHF₂ CH₂

A1.118 CF₃ CH₂OCH₂CH₂

A1.119 CF₂Cl CH₂OCH₂CH₂

A1.120 CHF₂ CH₂OCH₂CH₂

A1.121 CF₃ CH₂

A1.122 CF₂Cl CH₂

A1.123 CHF₂ CH₂

A1.124 CF₃ CH₂OCH₂CH₂

A1.125 CF₂Cl CH₂OCH₂CH₂

A1.126 CHF₂ CH₂OCH₂CH₂

A1.127 CF₃ CH₂

A1.128 CF₂Cl CH₂

A1.129 CHF₂ CH₂

A1.130 CF₃ CH₂OCH₂CH₂

A1.131 CF₂Cl CH₂OCH₂CH₂

A1.132 CHF₂ CH₂OCH₂CH₂

A1.133 CF₃ CH₂

A1.134 CF₂Cl CH₂

A1.135 CHF₂ CH₂

A1.136 CF₃ CH₂OCH₂CH₂

A1.137 CF₂Cl CH₂OCH₂CH₂

A1.138 CHF₂ CH₂OCH₂CH₂

A1.139 CF₃ CH₂

A1.140 CF₂Cl CH₂

A1.141 CHF₂ CH₂

A1.142 CF₃ CH₂OCH₂CH₂

A1.143 CF₂Cl CH₂OCH₂CH₂

A1.144 CHF₂ CH₂OCH₂CH₂

A1.145 CF₃ CH₂

A1.146 CF₂Cl CH₂

A1.147 CHF₂ CH₂

A1.148 CF₃ CH₂OCH₂CH₂

A1.149 CF₂Cl CH₂OCH₂CH₂

A1.150 CHF₂ CH₂OCH₂CH₂

A1.151 CF₃ CH₂

A1.152 CF₂Cl CH₂

A1.153 CHF₂ CH₂

A1.154 CF₃ CH₂OCH₂CH₂

A1.155 CF₂Cl CH₂OCH₂CH₂

A1.156 CHF₂ CH₂OCH₂CH₂

A1.157 CF₃ CH₂

A1.158 CF₂Cl CH₂

A1.159 CHF₂ CH₂

A1.160 CF₃ CH₂OCH₂CH₂

A1.161 CF₂Cl CH₂OCH₂CH₂

A1.162 CHF₂ CH₂OCH₂CH₂

A1.163 CF₃ CH₂

A1.164 CF₂Cl CH₂

A1.165 CHF₂ CH₂

A1.166 CF₃ CH₂OCH₂CH₂

A1.167 CF₂Cl CH₂OCH₂CH₂

A1.168 CHF₂ CH₂OCH₂CH₂

A1.169 CF₃ CH₂

A1.170 CF₂Cl CH₂

A1.171 CHF₂ CH₂

A1.172 CF₃ CH₂OCH₂CH₂

A1.173 CF₂Cl CH₂OCH₂CH₂

A1.174 CHF₂ CH₂OCH₂CH₂

A1.175 CF₃ CH₂

m.p.: 141° C. A1.176 CF₂Cl CH₂

A1.177 CHF₂ CH₂

A1.178 CF₃ CH₂OCH₂CH₂

A1.179 CF₂Cl CH₂OCH₂CH₂

A1.180 CHF₂ CH₂OCH₂CH₂

A1.181 CF₃ CH₂

m.p.: 151° C. A1.182 CF₂Cl CH₂

A1.183 CHF₂ CH₂

A1.184 CF₃ CH₂OCH₂CH₂

A1.185 CF₂Cl CH₂OCH₂CH₂

A1.186 CHF₂ CH₂OCH₂CH₂

A1.187 CF₃ CH₂

A1.188 CF₂Cl CH₂

A1.189 CHF₂ CH₂

A1.190 CF₃ CH₂OCH₂CH₂

A1.191 CF₂Cl CH₂OCH₂CH₂

A1.192 CHF₂ CH₂OCH₂CH₂

A1.193 CF₃ CH₂

solid A1.194 CF₂Cl CH₂

A1.195 CHF₂ CH₂

A1.196 CF₃ CH₂OCH₂CH₂

A1.197 CF₂Cl CH₂OCH₂CH₂

A1.198 CHF₂ CH₂OCH₂CH₂

A1.199 CF₃ CH₂

solid A1.200 CF₂Cl CH₂

A1.201 CHF₂ CH₂

A1.202 CF₃ CH₂

solid A1.203 CF₂Cl CH₂

A1.204 CHF₂ CH₂

A1.205 CF₃ CH₂OCH₂CH₂

A1.206 CF₂Cl CH₂OCH₂CH₂

A1.207 CHF₂ CH₂OCH₂CH₂

A1.208 CF₃ CH₂

resin A1.209 CF₃ CH₂

resin A1.210 CHF₂ CH₂

A1.211 CF₃ CH₂

solid A1.212 CHF₂ CH₂

A1.213 CF₃ CH₂

solid A1.214 CF₂Cl CH₂

A1.215 CF₃ CH₂

A1.216 CF₃ CH₂OCH₂CH₂

A1.217 CF₂Cl CH₂OCH₂CH₂

A1.218 CHF₂ CH₂OCH₂CH₂

A1.219 CF₃ CH₂

solid A1.220 CF₃ CH₂OCH₂CH₂

resin A1.221 CF₃ CH₂

resin A1.222 CF₃ CH₂

solid A1.223 CF₃ CH₂

solid A1.224 CF₃ CH₂

A1.225 CClF₂ CH₂

A1.226 CClF₂ CH₂

A1.227 CClF₂ CH₂

A1.228 CClF₂ CH₂

A1.229 CClF₂ CH₂

A1.230 CHF₂ CH₂

A1.231 CHF₂ CH₂

A1.232 CHF₂ CH₂

A1.233 CHF₂ CH₂

A1.234 CHF₂ CH₂

A1.235 CF₃ CH₂

m.p.: 181° C. A1.236 CHF₂ CH₂

A1.237 CF₃ CH₂

m.p.: 182° C. A1.238 CHF₂ CH₂

A1.240 CF₃ CH₂

m.p.: 157° C. A1.241 CHF₂ CH₂

A1.242 CF₃ CH₂

A1.243 CF₃ CH₂

A1.244 CF₃ CH₂

A1.245 CF₃ CH₂

resin; p = 1 (N-oxide)

TABLE A2 Compounds of formula IAa₂: (IAa₂)

Comp. No. R₃ L

Phys. data A2.001 CF₃ CH₂

A2.002 CF₂H CH₂

A2.003 CF₃ CH₂

A2.004 CF₃ CH₂

A2.005 CF₃ CH₂

A2.006 CF₃ CH₂

A2.007 CF₃ CH₂

A2.018 CF₃ CH₂

A2.019 CF₃ CH₂

A2.010 CF₃ CH₂

A2.011 CF₃ CH₂

A2.012 CF₃ CH₂

A2.013 CF₃ CH₂

A2.014 CF₃ CH₂

A2.015 CF₃ CH₂

A2.016 CF₃ CH₂

A2.017 CF₃ CH₂

A2.018 CF₃ CH₂

A2.019 CF₃ CH₂

A2.020 CF₃ CH₂

A2.021 CF₃ CH₂

A2.022 CF₃ CH₂

A2.023 CF₃ CH₂

TABLE A3 Compounds of formula IAa₃: (IAa₃)

Comp. No. R₃ L

Phys. data A3.001 CF₃ CH₂

A3.002 CF₂H CH₂

A3.003 CF₃ CH₂

A3.004 CF₃ CH₂

A3.005 CF₃ CH₂

A3.006 CF₃ CH₂

A3.007 CF₃ CH₂

A3.008 CF₃ CH₂

A3.009 CF₃ CH₂

A3.010 CF₃ CH₂

A3.011 CF₃ CH₂

A3.012 CF₃ CH₂

A3.013 CF₃ CH₂

A3.014 CF₃ CH₂

A3.015 CF₃ CH₂

A3.016 CF₃ CH₂

A3.017 CF₃ CH₂

A3.018 CF₃ CH₂

A3.019 CF₃ CH₂

A3.020 CF₃ CH₂

A3.021 CF₃ CH₂

A3.022 CF₃ CH₂

A3.023 CF₃ CH₂

TABLE A4 Compounds of formula IAa₄: (IAa₄)

Comp. No. R₃ L

Phys. data A4.001 CF₃ CH₂

A4.002 CF₂H CH₂

A4.003 CF₃ CH₂

A4.004 CF₃ CH₂

A4.005 CF₃ CH₂

A4.006 CF₃ CH₂

A4.007 CF₃ CH₂

A4.008 CF₃ CH₂

A4.009 CF₃ CH₂

A4.010 CF₃ CH₂

A4.011 CF₃ CH₂

A4.012 CF₃ CH₂

A4.013 CF₃ CH₂

A4.014 CF₃ CH₂

A4.015 CF₃ CH₂

A4.016 CF₃ CH₂

A4.017 CF₃ CH₂

A4.018 CF₃ CH₂

A4.019 CF₃ CH₂

A4.020 CF₃ CH₂

A4.021 CF₃ CH₂

A4.022 CF₃ CH₂

A4.023 CF₃ CH₂

TABLE A5 Compounds of formula IAa₅: (IAa₅)

Comp. No. R₃ L

Phys. data A5.001 CF₃ CH₂

A5.002 CF₂H CH₂

A5.003 CF₃ CH₂

A5.004 CF₃ CH₂

A5.005 CF₃ CH₂

A5.006 CF₃ CH₂

A5.007 CF₃ CH₂

A5.008 CF₃ CH₂

A5.009 CF₃ CH₂

A5.010 CF₃ CH₂

A5.011 CF₃ CH₂

A5.012 CF₃ CH₂

A5.013 CF₃ CH₂

A5.014 CF₃ CH₂

A5.015 CF₃ CH₂

A5.016 CF₃ CH₂

A5.017 CF₃ CH₂

A5.018 CF₃ CH₂

A5.019 CF₃ CH₂

A5.020 CF₃ CH₂

A5.021 CF₃ CH₂

A5.022 CF₃ CH₂

A5.023 CF₃ CH₂

TABLE A6 Compounds of formula IAa₆: (IAa₆)

Comp. No. R₃ L

Phys. data A6.001 CF₃ CH₂

A6.002 CF₂H CH₂

A6.003 CF₃ CH₂

A6.004 CF₃ CH₂OCH₂CH₂

A6.005 CF₂Cl CH₂OCH₂CH₂

A6.006 CHF₂ CH₂OCH₂CH₂

A6.007 CF₃ CH₂

A6.008 CF₂Cl CH₂

A6.009 CHF₂ CH₂

A6.010 CF₃ CH₂OCH₂CH₂

A6.011 CF₂Cl CH₂OCH₂CH₂

A6.012 CHF₂ CH₂OCH₂CH₂

A6.013 CF₃ CH₂

A6.014 CF₂Cl CH₂

A6.015 CHF₂ CH₂

A6.016 CF₃ CH₂OCH₂CH₂

A6.017 CF₂Cl CH₂OCH₂CH₂

A6.018 CHF₂ CH₂OCH₂CH₂

A6.019 CF₃ CH₂

A6.020 CF₂Cl CH₂

A6.021 CHF₂ CH₂

A6.022 CF₃ CH₂OCH₂CH₂

A6.023 CF₂Cl CH₂OCH₂CH₂

A6.024 CHF₂ CH₂OCH₂CH₂

A6.025 CF₃ CH₂

A6.026 CF₂Cl CH₂

A6.027 CHF₂ CH₂

A6.028 CF₃ CH₂OCH₂CH₂

A6.029 CF₂Cl CH₂OCH₂CH₂

A6.030 CHF₂ CH₂OCH₂CH₂

A6.031 CF₃ CH₂

A6.032 CF₂Cl CH₂

A6.033 CHF₂ CH₂

A6.034 CF₃ CH₂OCH₂CH₂

A6.035 CF₂Cl CH₂OCH₂CH₂

A6.036 CHF₂ CH₂OCH₂CH₂

A6.037 CF₃ CH₂

A6.038 CF₂Cl CH₂

A6.039 CHF₂ CH₂

A6.040 CF₃ CH₂OCH₂CH₂

A6.041 CF₂Cl CH₂OCH₂CH₂

A6.042 CHF₂ CH₂OCH₂CH₂

A6.043 CF₃ CH₂

A6.044 CF₂Cl CH₂

A6.045 CHF₂ CH₂

A6.046 CF₃ CH₂OCH₂CH₂

A6.047 CF₂Cl CH₂OCH₂CH₂

A6.048 CHF₂ CH₂OCH₂CH₂

A6.049 CF₃ CH₂

A6.050 CF₂Cl CH₂

A6.051 CHF₂ CH₂

A6.052 CF₃ CH₂OCH₂CH₂

A6.053 CF₂Cl CH₂OCH₂CH₂

A6.054 CHF₂ CH₂OCH₂CH₂

A6.055 CF₃ CH₂

resin A6.056 CF₂Cl CH₂

A6.057 CHF₂ CH₂

A6.058 CF₃ CH₂OCH₂CH₂

A6.059 CF₂Cl CH₂OCH₂CH₂

A6.060 CHF₂ CH₂OCH₂CH₂

A6.061 CF₃ CH₂

A6.062 CF₂Cl CH₂

A6.063 CHF₂ CH₂

A6.064 CF₃ CH₂OCH₂CH₂

A6.065 CF₂Cl CH₂OCH₂CH₂

A6.066 CHF₂ CH₂OCH₂CH₂

A6.067 CF₃ CH₂

A6.068 CF₂Cl CH₂

A6.069 CHF₂ CH₂

A6.070 CF₃ CH₂OCH₂CH₂

A6.071 CF₂Cl CH₂OCH₂CH₂

A6.072 CHF₂ CH₂OCH₂CH₂

A6.073 CF₃ CH₂

resin A6.074 CF₂Cl CH₂

A6.075 CHF₂ CH₂

A6.076 CF₃ CH₂OCH₂CH₂

A6.077 CF₂Cl CH₂OCH₂CH₂

A6.078 CHF₂ CH₂OCH₂CH₂

A6.079 CF₃ CH₂

amorphous crystals A6.080 CF₂Cl CH₂

A6.081 CHF₂ CH₂

A6.082 (P3) CF₃ CH₂OCH₂CH₂

resin A6.083 CF₂Cl CH₂OCH₂CH₂

A6.084 CHF₂ CH₂OCH₂CH₂

A6.085 CF₃ CH₂

amorphous crystals A6.086 CF₂Cl CH₂

A6.087 CHF₂ CH₂

A6.088 CF₃ CH2QCH₂CH₂

A6.089 CF₂Cl CH₂OCH₂CH₂

A6.090 CHF₂ CH₂OCH₂CH₂

A6.091 CF₃ CH₂

resin A6.092 CF₂Cl CH₂

A6.093 CHF₂ CH₂

A6.094 CF₃ CH₂OCH₂CH₂

A6.095 CF₂Cl CH₂OCH₂CH₂

A6.096 CHF₂ CH₂OCH₂CH₂

A6.097 CF₃ CH₂

amorphous crystals A6.098 CF₂Cl CH₂

A6.099 CHF₂ CH₂

A6.100 CF₃ CH₂OCH₂CH₂

resin A6.101 CF₂Cl CH₂OCH₂CH₂

A6.102 CHF₂ CH₂OCH₂CH₂

A6.103 CF₃ CH₂

A6.104 CF₂Cl CH₂

A6.105 CHF₂ CH₂

A6.106 CF₃ CH₂OCH₂CH₂

A6.107 CF₂Cl CH₂OCH₂CH₂

A6.108 CHF₂ CH₂OCH₂CH₂

A6.109 CF₃ CH₂

A6.110 CF₂Cl CH₂

A6.111 CHF₂ CH₂

A6.112 CF₃ CH₂OCH₂CH₂

A6.113 CF₂Cl CH₂OCH₂CH₂

A6.114 CHF₂ CH₂OCH₂CH₂

A6.115 CF₃ CH₂

A6.116 CF₂Cl CH₂

A6.117 CHF₂ CH₂

A6.118 CF₃ CH₂OCH₂CH₂

A6.119 CF₂Cl CH₂OCH₂CH₂

A6.120 CHF₂ CH₂OCH₂CH₂

A6.121 CF₃ CH₂

A6.122 CF₂Cl CH₂

A6.123 CHF₂ CH₂

A6.124 CF₃ CH₂OCH₂CH₂

A6.125 CF₂Cl CH₂OCH₂CH₂

A6.126 CHF₂ CH₂OCH₂CH₂

A6.127 CF₃ CH₂

A6.128 CF₂Cl CH₂

A6.129 CHF₂ CH₂

A6.130 CF₃ CH₂OCH₂CH₂

A6.131 CF₂Cl CH₂OCH₂CH₂

A6.132 CHF₂ CH₂OCH₂CH₂

A6.133 CF₃ CH₂

A6.134 CF₂Cl CH₂

A6.135 CHF₂ CH₂

A6.136 CF₃ CH₂OCH₂CH₂

A6.137 CF₂Cl CH₂OCH₂CH₂

A6.138 CHF₂ CH₂OCH₂CH₂

A6.139 CF₃ CH₂

A6.140 CF₂Cl CH₂

A6.141 CHF₂ CH₂

A6.142 CF₃ CH₂OCH₂CH₂

A6.143 CF₂Cl CH₂OCH₂CH₂

A6.144 CHF₂ CH₂OCH₂CH₂

A6.145 CF₃ CH₂

A6.146 CF₂Cl CH₂

A6.147 CHF₂ CH₂

A6.148 CF₃ CH₂OCH₂CH₂

A6.149 CF₂Cl CH₂OCH₂CH₂

A6.150 CHF₂ CH₂OCH₂CH₂

A6.151 CF₃ CH₂

A6.152 CF₂Cl CH₂

A6.153 CHF₂ CH₂

A6.154 CF₃ CH₂OCH₂CH₂ ~

A6.155 CF₂Cl CH₂OCH₂CH₂

A6.156 CHF₂ CH₂OCH₂CH₂

A6.157 CF₃ CH₂

A6.158 CF₂Cl CH₂

A6.159 CHF₂ CH₂

A6.160 CF₃ CH₂OCH₂CH₂

A6.161 CF₂Cl CH₂OCH₂CH₂

A6.162 CHF₂ CH₂OCH₂CH₂

A6.163 CF₃ CH₂

A6.164 CF₂Cl CH₂

A6.165 CHF₂ CH₂

A6.166 CF₃ CH₂OCH₂CH₂

A6.167 CF₂Cl CH₂OCH₂CH₂

A6.168 CHF₂ CH₂OCH₂CH₂

A6.169 CF₃ CH₂

A6.170 CF₂Cl CH₂

A6.171 CHF₂ CH₂

A6.172 CF₃ CH₂OCH₂CH₂

A6.173 CF₂Cl CH₂OCH₂CH₂

A6.174 CHF₂ CH₂OCH₂CH₂

A6.175 CF₃ CH₂

A6.176 CF₂Cl CH₂

A6.177 CHF₂ CH₂

A6.178 CF₃ CH₂OCH₂CH₂

A6.179 CF₂Cl CH₂OCH₂CH₂

A6.180 CHF₂ CH₂OCH₂CH₂

A6.181 CF₃ CH₂

m.p.: 134° C. A6.182 CF₂Cl CH₂

A6.183 CHF₂ CH₂

A6.184 CF₃ CH₂OCH₂CH₂

A6.185 CF₂Cl CH₂OCH₂CH₂

A6.186 CHF₂ CH₂OCH₂CH₂

A6.187 CF₃ CH₂

A6.188 CF₂Cl CH₂

A6.189 CHF₂ CH₂

A6.190 CF₃ CH₂OCH₂CH₂

A6.191 CF₂Cl CH₂OCH₂CH₂

A6.192 CHF₂ CH₂OCH₂CH₂

A6.193 CF₃ CH₂

A6.194 CF₂Cl CH₂

A6.195 CHF₂ CH₂

A6.196 CF₃ CH₂OCH₂CH₂

A6.197 CF₂Cl CH₂OCH₂CH₂

A6.198 CHF₂ CH₂OCH₂CH₂

A6.199 CF₃ CH₂

A6.200 CF₂Cl CH₂

A6.201 CHF₂ CH₂

A6.202 CF₃ CH₂

A6.203 CF₂Cl CH₂

A6.204 CHF₂ CH₂

A6.205 CF₃ CH₂OCH₂CH₂

A6.206 CF₂Cl CH₂OCH₂CH₂

A6.207 CHF₂ CH₂OCH₂CH₂

A6.208 CF₃ CH₂

resin A6.209 CF₃ CH₂

A6.210 CHF₂ CH₂

A6.211 CF₃ CH₂

A6.212 CHF₂ CH₂

A6.213 CF₃ CH₂

A6.214 CF₂Cl CH₂

A6.215 CHF₂ CH₂

A6.216 CF₃ CH₂OCH₂CH₂

A6.217 CF₂Cl CH₂OCH₂CH₂

A6.218 CHF₂ CH₂OCH₂CH₂

A6.219 CH₂ CF₃

A6.220 CH₂ CF₂Cl

A6.221 CH₂ CHF₂

A6.222 CH₂OCH₂CH₂ CF₃

A6.223 CH₂OCH₂CH₂ CF₂Cl

A6.224 CH₂OCH₂CH₂ CHF₂

A6.225 CF₃ CH₂

A6.226 CF₃ CH₂OCH₂CH₂

A6.227 CF₃ CH₂

A6.228 CF₃ CH₂

A6.229 CF₃ CH₂

A6.230 CClF₂ CH₂

A6.231 CClF₂ CH₂

A6.232 CClF₂

A6.233 CClF₂

A6.234 CHF₂

A6.235 CHF₂

A6.236 CHF₂

A6.237 CHF₂

A6.238 CF₃ CH₂

resin A6.239 CHF₂ CH₂

A6.240 CF₃ CH₂

m.p.: 113° C. A6.241 CHF₂ CH₂

A6.242 CF₃ CH₂

resin A6.243 CHF₂ CH₂

A6.244 CF₃ CH₂

A6.245 CF₃ CH₂

A6.246 CF₃ CH₂

A6.247 CF₃ CH₂OCH₂CH₂

resin; p = 1 (N-oxide)

TABLE A7 Compounds of formula IAa₇: (IAa₇)

Comp. No. R₃ L

Phys. data A7.001 CF₃ CH₂

A7.002 CF₂H CH₂

A7.003 CF₃ CH₂

A7.004 CF₃ CH₂

A7.005 CF₃ CH₂

A7.006 CF₃ CH₂

A7.007 CF₃ CH₂

A7.008 CF₃ CH₂

amorphous crystals A7.009 CF₃ CH₂

amorphous crystals A7.010 CF₃ CH₂

A7.011 CF₃ CH₂OCH₂CH₂

A7.012 CF₃ CH₂OCH₂CH₂

A7.013 CF₃ CH₂

A7.014 CF₃ CH₂

A7.015 CF₃ CH₂

A7.016 CF₃ CH₂

A7.017 CF₃ CH₂

A7.018 CF₃ CH₂

A7.019 CF₃ CH₂

A7.020 CF₃ CH₂

A7.021 CF₃ CH₂

A7.022 CF₃ CH₂

A7.023 CF₃ CH₂

A7.024 CF₃ CH₂

A7.025 CF₃ CH₂

A7.026 CF₃ CH₂

resin; p = 1 (N-oxide)

TABLE 8 Compounds of formula IAa₈: (IAa₈)

Comp. No. R₃ L

Phys. data A8.001 CF₃ CH₂

A8.002 CF₂H CH₂

A8.003 CF₃ CH₂

A8.004 CF₃ CH₂

A8.005 CF₃ CH₂

A8.006 CF₃ CH₂

A8.007 CF₃ CH₂

A8.008 CF₃ CH₂

solid A8.009 CF₃ CH₂

A8.010 CF₃ CH₂

A8.011 CF₃ CH₂OCH₂CH₂

A8.012 CF₃ CH₂OCH₂CH₂

A8.013 CF₃ CH₂

A8.014 CF₂Cl CH₂

A8.015 CF₂H CH₂

A8.016 CF₃ CH₂OCH₂CH₂

A8.017 CF₂Cl CH₂OCH₂CH₂

A8.018 CHF₂ CH₂OCH₂CH₂

A8.019 CF₂Cl CH₂

A8.020 CF₃ CH₂OCH₂CH₂

A8.021 CF₂Cl CH₂OCH₂CH₂

A8.022 CHF₂ CH₂OCH₂CH₂

A8.023 CF₂Cl CH₂

A8.024 CHF₂ CH₂

A8.025 CF₃ CH₂OCH₂CH₂

A8.026 CF₂Cl CH₂OCH₂CH₂

A8.027 CHF₂ CH₂OCH₂CH₂

A8.028 CF₂Cl CH₂

A8.029 CHF₂ CH₂

A8.030 CF₃ CH₂OCH₂CH₂

A8.031 CF₂Cl CH₂OCH₂CH₂

A8.032 CHF₂ CH₂OCH₂CH₂

A8.033 CF₃ CH₂

A8.034 CF₂Cl CH₂

A8.035 CHF₂ CH₂

A8.036 CF₃ CH₂OCH₂CH₂

A8.037 CF₂Cl CH₂OCH₂CH₂

A8.038 CHF₂ CH₂OCH₂CH₂

A8.039 CF₃ CH₂

A8.040 CF₂Cl CH₂

A8.041 CHF₂ CH₂

A8.042 CF₃ CH₂OCH₂CH₂

A8.043 CF₂Cl CH₂OCH₂CH₂

A8.044 CHF₂ CH₂OCH₂CH₂

A8.050 CF₃ CH₂

A8.051 CF₂Cl CH₂

A8.052 CHF₂ CH₂

A8.053 CF₃ CH₂OCH₂CH₂

A8.054 CF₂Cl CH₂OCH₂CH₂

A8.055 CHF₂ CH₂OCH₂CH₂

A8.056 CF₃ CH₂

A8.057 CF₂Cl CH₂

A8.058 CHF₂ CH₂

A8.059 CF₃ CH₂OCH₂CH₂

A8.060 CF₂Cl CH₂OCH₂CH₂

A8.061 CHF₂ CH₂OCH₂CH₂

A8.062 CF₃ CH₂

resin A8.063 CF₂Cl CH₂

A8.064 CHF₂ CH₂

A8.065 CF₃ CH₂OCH₂CH₂

A8.066 CF₂Cl CH₂OCH₂CH₂

A8.067 CHF₂ CH₂OCH₂CH₂

A8.068 CF₃ CH₂

A8.069 CF₂Cl CH₂

A8.070 CHF₂ CH₂

A8.071 CF₃ CH₂OCH₂CH₂

A8.072 CF₂Cl CH₂OCH₂CH₂

A8.073 CHF₂ CH₂OCH₂CH₂

A8.074 CF₃ CH₂

A8.075 CF₂Cl CH₂

A8.076 CHF₂ CH₂

A8.077 CF₃ CH₂OCH₂CH₂

A8.078 CF₂Cl CH₂OCH₂CH₂

A8.079 CHF₂ CH₂OCH₂CH₂

A8.080 CF₃ CH₂

resin A8.081 CF₂Cl CH₂

A8.082 CHF₂ CH₂

A8.083 CF₃ CH₂OCH₂CH₂

A8.084 CF₂Cl CH₂OCH₂CH₂

A8.085 CHF₂ CH₂OCH₂CH₂

A8.086 CF₂Cl CH₂

A8.087 CHF₂ CH₂

A8.088 CF₂Cl CH₂OCH₂CH₂

A8.089 CHF₂ CH₂OCH₂CH₂

A8.090 CF₂Cl CH₂

A8.091 CHF₂ CH₂

A8.092 CF₃ CH₂OCH₂CH₂

A8.093 CF₂Cl CH₂OCH₂CH₂

A8.094 CHF₂ CH₂OCH₂CH₂

A8.095 CF₃ CH₂

resin A8.096 CF₂Cl CH₂

A8.097 CHF₂ CH₂

A8.098 CF₃ CH₂OCH₂CH₂

A8.099 CF₂Cl CH₂OCH₂CH₂

A8.100 CHF₂ CH₂OCH₂CH₂

A8.101 CF₂Cl CH₂

A8.102 CHF₂ CH₂

A8.103 CF₂Cl CH₂OCH₂CH₂

A8.104 CHF₂ CH₂OCH₂CH₂

A8.105 CF₃ CH₂

A8.106 CF₂Cl CH₂

A8.107 CHF₂ CH₂

A8.108 CF₃ CH₂OCH₂CH₂

A8.109 CF₂Cl CH₂OCH₂CH₂

A8.110 CHF₂ CH₂OCH₂CH₂

A8.111 CF₃ CH₂

A8.112 CF₂Cl CH₂

A8.113 CHF₂ CH₂

A8.114 CF₃ CH₂OCH₂CH₂

A8.115 CF₂Cl CH₂OCH₂CH₂

A8.116 CHF₂ CH₂OCH₂CH₂

A8.117 CF₃ CH₂

A8.118 CF₂Cl CH₂

A8.119 CHF₂ CH₂

A8.120 CF₃ CH₂OCH₂CH₂

A8.121 CF₂Cl CH₂OCH₂CH₂

A8.122 CHF₂ CH₂OCH₂CH₂

A8.123 CF₃ CH₂

A8.124 CF₂Cl CH₂

A8.125 CHF₂ CH₂

A8.126 CF₃ CH₂OCH₂CH₂

A8.127 CF₂Cl CH₂OCH₂CH₂

A8.128 CHF₂ CH₂OCH₂CH₂

A8.129 CF₃ CH₂

A8.130 CF₂Cl CH₂

A8.131 CHF₂ CH₂

A8.132 CF₃ CH₂OCH₂CH₂

A8.133 CF₂Cl CH₂OCH₂CH₂

A8.134 CHF₂ CH₂OCH₂CH₂

A8.135 CF₃ CH₂

A8.136 CF₂Cl CH₂

A8.137 CHF₂ CH₂

A8.138 CF₃ CH₂OCH₂CH₂

A8.139 CF₂Cl CH₂OCH₂CH₂

A8.140 CHF₂ CH₂OCH₂CH₂

A8.141 CF₂Cl CH₂

A8.142 CHF₂ CH₂

A8.143 CF₃ CH₂OCH₂CH₂

A8.144 CF₂Cl CH₂OCH₂CH₂

A8.145 CHF₂ CH₂OCH₂CH₂

A8.146 CF₂Cl CH₂

A8.147 CHF₂ CH₂

A8.148 CF₃ CH₂OCH₂CH₂

A8.149 CF₂Cl CH₂OCH₂CH₂

A8.150 CHF₂ CH₂OCH₂CH₂

A8.151 CF₂Cl CH₂

A8.152 CHF₂ CH₂

A8.153 CF₃ CH₂OCH₂CH₂

A8.154 CF₂Cl CH₂OCH₂CH₂

A8.155 CHF₂ CH₂OCH₂CH₂

A8.156 CF₃ CH₂

A8.157 CF₂Cl CH₂

A8.158 CHF₂ CH₂

A8.159 CF₃ CH₂OCH₂CH₂

A8.160 CF₂Cl CH₂OCH₂CH₂

A8.161 CHF₂ CH₂OCH₂CH₂

A8.162 CF₃ CH₂

A8.163 CF₂Cl CH₂

A8.164 CHF₂ CH₂

A8.165 CF₃ CH₂OCH₂CH₂

A8.166 CF₂Cl CH₂OCH₂CH₂

A8.167 CHF₂ CH₂OCH₂CH₂

A8.168 CF₃ CH₂

m.p.: 65° C. A8.169 CF₂Cl CH₂

A8.170 CHF₂ CH₂

A8.171 CF₃ CH₂OCH₂CH₂

A8.172 CF₂Cl CH₂OCH₂CH₂

A8.173 CHF₂ CH₂OCH₂CH₂

A8.174 CF₃ CH₂

resin A8.175 CF₂Cl CH₂

A8.176 CHF₂ CH₂

A8.177 CF₃ CH₂OCH₂CH₂

A8.178 CF₂Cl CH₂OCH₂CH₂

A8.179 CHF₂ CH₂OCH₂CH₂

A8.180 CF₃ CH₂

A8.181 CF₂Cl CH₂

A8.182 CHF₂ CH₂

A8.183 CF₃ CH₂OCH₂CH₂

A8.184 CF₂Cl CH₂OCH₂CH₂

A8.185 CHF₂ CH₂OCH₂CH₂

A8.186 CF₃ CH₂

A8.187 CF₂Cl CH₂

A8.188 CHF₂ CH₂

A8.189 CF₃ CH₂OCH₂CH₂

A8.190 CF₂Cl CH₂OCH₂CH₂

A8.191 CHF₂ CH₂OCH₂CH₂

A8.192 CF₃ CH₂

A8.193 CF₂Cl CH₂

A8.194 CHF₂ CH₂

A8.195 CF₃ CH₂

A8.196 CF₂Cl CH₂

A8.197 CHF₂ CH₂

A8.198 CF₃ CH₂OCH₂CH₂

A8.199 CF₂Cl CH₂OCH₂CH₂

A8.200 CHF₂ CH₂OCH₂CH₂

A8.201 CF₃ CH₂

A8.202 CF₂Cl CH₂

A8.203 CHF₂ CH₂

A8.204 CF₃ CH₂

resin A8.205 CF₃ CH₂

A8.206 CF₃ CH₂OCH₂CH₂

A8.207 CF₃ CH₂

A8.208 CF₃ CH₂

A8.209 CF₃ CH₂

A8.210 CClF₂ CH₂

A8.211 CClF₂ CH₂

A8.212 CClF₂ CH₂

A8.213 CClF₂ CH₂

A8.214 CHF₂ CH₂

A8.215 CHF₂ CH₂

A8.216 CHF₂ CH₂

A8.217 CHF₂ CH₂

A8.218 CF₃ CH₂

resin A8.219 CHF₂ CH₂

A8.220 CF₃ CH₂

m.p.: 69° C. A8.221 CHF₂ CH₂

A8.222 CF₃ CH₂

A8.223 CHF₂ CH₂

A8.224 CF₃ CH₂

A8.225 CF₃ CH₂

A8.226 CF₃ CH₂

TABLE A9 Compounds of formula IAa₉: (IAa₉)

Comp. No. R₃ L

Phys. data A9.001 CF₃ CH₂

A9.002 CF₂H CH₂

A9.003 CF₃ CH₂

A9.004 CF₃ CH₂

A9.005 CF₃ CH₂

A9.006 CF₃ CH₂

A9.007 CF₃ CH₂

A9.008 CF₃ CH₂

A9.009 CF₃ CH₂

A9.010 CF₃ CH₂

A9.011 CF₃ CH₂

A9.012 CF₃ CH₂

A9.013 CF₃ CH₂

A9.014 CF₃ CH₂

A9.015 CF₃ CH₂

A9.016 CF₃ CH₂

A9.017 CF₃ CH₂

A9.018 CF₃ CH₂

A9.019 CF₃ CH₂

A9.020 CF₃ CH₂

A9.021 CF₃ CH₂

A9.022 CF₃ CH₂

A9.023 CF₃ CH₂

TABLE A10 Compounds of formula IAa₁₀: (IAa₉)

Comp. No. R₃ L

Phys. data A10.001 CF₃ CH₂

A10.002 CF₂H CH₂

A10.003 CF₃ CH₂

A10.004 CF₃ CH₂

A10.005 CF₃ CH₂

A10.006 CF₃ CH₂

A10.007 CF₃ CH₂

A10.008 CF₃ CH₂

A10.009 CF₃ CH₂

A10.010 CF₃ CH₂

A10.011 CF₃ CH₂

A10.012 CF₃ CH₂

A10.013 CF₃ CH₂

A10.014 CF₃ CH₂

A10.015 CF₃ CH₂

A10.016 CF₃ CH₂

A10.017 CF₃ CH₂

A10.018 CF₃ CH₂

A10.019 CF₃ CH₂

A10.020 CF₃ CH₂

A10.021 CF₃ CH₂

A10.022 CF₃ CH₂

TABLE B1 Compounds of formula IAb₁: (IAb₁)

Comp. No. R₃ L

Phys. data B1.001 CF₃ CH₂

solid B1.002 CF₂H CH₂

B1.003 CF₃ CH₂

B1.004 CF₃ CH₂

solid B1.005 CF₃ CH₂

solid B1.006 CF₃ CH₂

B1.007 CF₃ CH₂

B1.008 CF₃ CH₂

m.p.: 173°C. B1.009 CF₃ CH₂

B1.010 CF₃ CH₂

B1.011 CF₃ CH₂OCH₂CH₂

B1.012 CF₃ CH₂OCH₂CH₂

B1.013 CF₃ CH₂

B1.014 CF₂Cl CH₂

B1.015 CF₂H CH₂

B1.016 CF₃ CH₂OCH₂CH₂

B1.017 CF₂Cl CH₂OCH₂CH₂

B1.018 CHF₂ CH₂OCH₂CH₂

B1.019 CF₂Cl CH₂

B1.020 CF₃ CH₂OCH₂CH₂

B1.021 CF₂Cl CH₂OCH₂CH₂

B1.022 CHF₂ CH₂OCH₂CH₂

B1.023 CF₂Cl CH₂

B1.024 CHF₂ CH₂

B1.025 CF₃ CH₂OCH₂CH₂

B1.026 CF₂Cl CH₂OCH₂CH₂

B1.027 CHF₂ CH₂OCH₂CH₂

B1.028 CF₂Cl CH₂

B1.029 CHF₂ CH₂

B1.030 CF₃ CH₂OCH₂CH₂

B1.031 CF₂Cl CH₂OCH₂CH₂

B1.032 CHF₂ CH₂OCH₂CH₂

B1.033 CF₃ CH₂

solid B1.034 CF₂Cl CH₂

B1.035 CHF₂ CH₂

B1.036 CF₃ CH₂OCH₂CH₂

B1.037 CF₂Cl CH₂OCH₂CH₂

B1.038 CHF₂ CH₂OCH₂CH₂

B1.039 CF₃ CH₂

solid B1.040 CF₂Cl CH₂

B1.041 CHF₂ CH₂

B1.042 CF₃ CH₂OCH₂CH₂

B1.043 CF₂Cl CH₂OCH₂CH₂

B1.044 CHF₂ CH₂OCH₂CH₂

B1.050 CF₃ CH₂

solid B1.051 CF₂Cl CH₂

B1.052 CHF₂ CH₂

B1.053 CF₃ CH₂OCH₂CH₂

B1.054 CF₂Cl CH₂OCH₂CH₂

B1.055 CHF₂ CH₂OCH₂CH₂

B1.056 CF₃ CH₂

solid B1.057 CF₂Cl CH₂

B1.058 CHF₂ CH₂

B1.059 CF₃ CH₂OCH₂CH₂

B1.060 CF₂Cl CH₂OCH₂CH₂

B1.061 CHF₂ CH₂OCH₂CH₂

B1.062 CF₃ CH₂

m.p.: 173°C. B1.063 CF₂Cl CH₂

B1.064 CHF₂ CH₂

B1.065 CF₃ CH₂OCH₂CH₂

B1.066 CF₂Cl CH₂OCH₂CH₂

B1.067 CHF₂ CH₂OCH₂CH₂

B1.068 CF₃ CH₂

B1.069 CF₂Cl CH₂

B1.070 CHF₂ CH₂

B1.071 CF₃ CH₂OCH₂CH₂

B1.072 CF₂Cl CH₂OCH₂CH₂

B1.073 CHF₂ CH₂OCH₂CH₂

B1.074 CF₃ CH₂

B1.075 CF₂Cl CH₂

B1.076 CHF₂ CH₂

B1.077 CF₃ CH₂OCH₂CH₂

B1.078 CF₂Cl CH₂OCH₂CH₂

B1.079 CHF₂ CH₂OCH₂CH₂

B1.080 CF₃ CH₂

solid B1.081 CF₂Cl CH₂

B1.082 CHF₂ CH₂

B1.083 CF₃ CH₂OCH₂CH₂

B1.084 CF₂Cl CH₂OCH₂CH₂

B1.085 CHF₂ CH₂OCH₂CH₂

B1.086 CF₂Cl CH₂

B1.087 CHF₂ CH₂

B1.088 CF₃ CH₂OCH₂CH₂

B1.089 CF₂Cl CH₂OCH₂CH₂

B1.090 CHF₂ CH₂OCH₂CH₂

B1.091 CF₂Cl CH₂

B1.092 CHF₂ CH₂

B1.093 CF₃ CH₂OCH₂CH₂

B1.094 CF₂Cl CH₂OCH₂CH₂

B1.095 CHF₂ CH₂OCH₂CH₂

B1.096 CF₃ CH₂

solid B1.097 CF₂Cl CH₂

B1.098 CHF₂ CH₂

B1.099 CF₃ CH₂OCH₂CH₂

B1.100 CF₂Cl CH₂OCH₂CH₂

B1.101 CHF₂ CH₂OCH₂CH₂

B1.102 CF₂Cl CH₂

B1.103 CHF₂ CH₂

B1.104 CF₂ CH₂OCH₂CH₂

B1.105 CF₂Cl CH₂OCH₂CH₂

B1.106 CHF₂ CH₂OCH₂CH₂

B1.107 CF₃ CH₂

B1.108 CF₂Cl CH₂

B1.109 CHF₂ CH₂

B1.110 CF₃ CH₂OCH₂CH₂

B1.111 CF₂Cl CH₂OCH₂CH₂

B1.112 CHF₂ CH₂OCH₂CH₂

B1.113 CF₃ CH₂

B1.114 CF₂Cl CH₂

B1.115 CHF₂ CH₂

B1.116 CF₃ CH₂OCH₂CH₂

B1.117 CF₂Cl CH₂OCH₂CH₂

B1.118 CHF₂ CH₂OCH₂CH₂

B1.119 CF₃ CH₂

B1.120 CF₂Cl CH₂

B1.121 CHF₂ CH₂

B1.122 CF₃ CH₂OCH₂CH₂

B1.123 CF₂Cl CH₂OCH₂CH₂

B1.124 CHF₂ CH₂OCH₂CH₂

B1.125 CF₃ CH₂

B1.126 CF₂Cl CH₂

B1.127 CHF₂ CH₂

B1.128 CF₃ CH₂OCH₂CH₂

B1.129 CF₂Cl CH₂OCH₂CH₂

B1.130 CHF₂ CH₂OCH₂CH₂

B1.131 CF₃ CH₂

B1.132 CF₂Cl CH₂

B1.133 CHF₂ CH₂

B1.134 CF₃ CH₂OCH₂CH₂

B1.135 CF₂Cl CH₂OCH₂CH₂

B1.136 CHF₂ CH₂OCH₂CH₂

B1.137 CF₃ CH₂

B1.138 CF₂Cl CH₂

B1.139 CHF₂ CH₂

B1.140 CF₃ CH₂OCH₂CH₂

B1.141 CF₂Cl CH₂OCH₂CH₂

B1.142 CHF₂ CH₂OCH₂CH₂

B1.143 CF₂Cl CH₂

B1.144 CHF₂ CH₂

B1.145 CF₃ CH₂OCH₂CH₂

B1.146 CF₂Cl CH₂OCH₂CH₂

B1.147 CHF₂ CH₂OCH₂CH₂

B1.148 CF₂Cl CH₂

B1.149 CHF₂ CH₂

B1.150 CF₃ CH₂OCH₂CH₂

B1.151 CF₂Cl CH₂OCH₂CH₂

B1.152 CHF₂ CH₂OCH₂CH₂

B1.153 CF₂Cl CH₂

B1.154 CHF₂ CH₂

B1.155 CF₃ CH₂OCH₂CH₂

B1.156 CF₂Cl CH₂OCH₂CH₂

B1.157 CHF₂ CH₂OCH₂CH₂

B1.158 CF₃ CH₂

resin B1.159 CF₂Cl CH₂

B1.160 CHF₂ CH₂

B1.161 CF₃ CH₂OCH₂CH₂

B1.162 CF₂Cl CH₂OCH₂CH₂

B1.163 CHF₂ CH₂OCH₂CH₂

B1.164 CF₃ CH₂

B1.165 CF₂Cl CH₂

B1.166 CHF₂ CH₂

B1.167 CF₃ CH₂OCH₂CH₂

B1.168 CF₂Cl CH₂OCH₂CH₂

B1.169 CHF₂ CH₂OCH₂CH₂

B1.170 CF₃ CH₂

m.p.: 171°C. B1.171 CF₂Cl CH₂

B1.172 CHF₂ CH₂

B1.173 CF₃ CH₂OCH₂CH₂

B1.174 CF₂Cl CH₂OCH₂CH₂

B1.175 CHF₂ CH₂OCH₂CH₂

B1.176 CF₃ CH₂

solid B1.177 CF₂Cl CH₂

B1.178 CHF₂ CH₂

B1.179 CF₃ CH₂OCH₂CH₂

B1.180 CF₂Cl CH₂OCH₂CH₂

B1.181 CHF₂ CH₂OCH₂CH₂

B1.182 CF₃ CH₂

B1.183 CF₂Cl CH₂

B1.184 CHF₂ CH₂

B1.185 CF₃ CH₂OCH₂CH₂

B1.186 CF₂Cl CH₂OCH₂CH₂

B1.187 CHF₂ CH₂OCH₂CH₂

B1.188 CF₃ CH₂

solid B1.189 CF₂Cl CH₂

B1.190 CHF₂ CH₂

B1.191 CF₃ CH₂OCH₂CH₂

B1.192 CF₂Cl CH₂OCH₂CH₂

B1.193 CHF₂ CH₂OCH₂CH₂

B1.194 CF₃ CH₂

solid B1.195 CF₂Cl CH₂

B1.196 CHF₂ CH₂

B1.197 CF₃ CH₂

B1.198 CF₂Cl CH₂

B1.199 CHF₂ CH₂

B1.200 CF₃ CH₂OCH₂CH₂

B1.201 CF₂Cl CH₂OCH₂CH₂

B1.202 CHF₂ CH₂OCH₂CH₂

B1.203 CF₃ CH₂

B1.204 CF₂Cl CH₂

B1.205 CHF₂ CH₂

B1.206 CF₃ CH₂

B1.207 CF₃ CH₂

B1.208 CF₂Cl CH₂

B1.209 CF₃ CH₂

B1.210 CF₂Cl CH₂

B1.211 CF₃ CH₂

solid B1.212 CF₂Cl CH₂

B1.213 CHF₂ CH₂

B1.214 CF₃ CH₂OCH₂CH₂

B1.215 CF₂Cl CH₂OCH₂CH₂

B1.216 CHF₂ CH₂OCH₂CH₂

B1.217 CH₂ CF₃

B1.218 CH₂ CF₂Cl

B1.219 CH₂ CHF₂

B1.220 CH₂OCH_(2 CH) ₂ CF₃

B1.221 CH₂OCH_(2 CH) ₂ CF₂Cl

B1.222 CH₂OCH_(2 CH) ₂ CHF₂

B1.223 CF₃ CH₂

solid B1.224 CF₃ CH₂OCH₂CH₂

resin B1.225 CF₃ CH₂

solid B1.226 CF₃ CH₂

solid B1.227 CF₃ CH₂

solid B1.228 CClF₂ CH₂

B1.229 CClF₂ CH₂

B1.230 CClF₂ CH₂

B1.231 CClF₂ CH₂

B1.232 CHF₂ CH₂

B1.233 CHF₂ CH₂

B1.234 CHF₂ CH₂

B1.235 CHF₂ CH₂

B1.236 CF₃ CH₂

resin B1.237 CHF₂ CH₂

B1.238 CF₃ CH₂

solid B1.239 CHF₂ CH₂

B1.240 CF₃ CH₂

m.p.: 192°C. B1.241 CHF₂ CH₂

B1.242 CF₃ CH₂

B1.243 CF₃ CH₂

B1.244 CF₃ CH₂

TABLE B2 Compounds of formula IAb₂: (IAb₂)

Phys. Comp. No. R₃ L

data B2.001 CF₃ CH₂

B2.002 CF₂H CH₂

B2.003 CF₃ CH₂

B2.004 CF₃ CH₂

B2.005 CF₃ CH₂

B2.006 CF₃ CH₂

B2.007 CF₃ CH₂

B2.008 CF₃ CH₂

B2.009 CF₃ CH₂

B2.010 CF₃ CH₂

B2.011 CF₃ CH₂

B2.012 CF₃ CH₂

B2.013 CF₃ CH₂

B2.014 CF₃ CH₂

B2.015 CF₃ CH₂

B2.016 CF₃ CH₂

B2.017 CF₃ CH₂

B2.018 CF₃ CH₂

B2.019 CF₃ CH₂

B2.020 CF₃ CH₂

B2.021 CF₃ CH₂

B2.022 CF₃ CH₂

B2.023 CF₃ CH₂

TABLE B3 Compounds of formula IAb₃: (IAb₃)

Phys. Comp. No. R₃ L

data B3.001 CF₃ CH₂

B3.002 CF₂H CH₂

B3.003 CF₃ CH₂

B3.004 CF₃ CH₂

B3.005 CF₃ CH₂

B3.006 CF₃ CH₂

B3.007 CF₃ CH₂

B3.008 CF₃ CH₂

B3.009 CF₃ CH₂

B3.010 CF₃ CH₂

B3.011 CF₃ CH₂

B3.012 CF₃ CH₂

B3.013 CF₃ CH₂

B3.014 CF₃ CH₂

B3.015 CF₃ CH₂

B3.016 CF₃ CH₂

B3.017 CF₃ CH₂

B3.018 CF₃ CH₂

B3.019 CF₃ CH₂

B3.020 CF₃ CH₂

B3.021 CF₃ CH₂

B3.022 CF₃ CH₂

TABLE C1 Compounds of formula IAc₁: (IAc₁)

Phys. Comp. No. R₃ L

data C1.001 CF₃ CH₂

C1.002 CF₂H CH₂

C1.003 CF₃ CH₂

C1.004 CF₃ CH₂

C1.005 CF₃ CH₂

C1.006 CF₃ CH₂

C1.007 CF₃ CH₂

C1.008 CF₃ CH₂

C1.009 CF₃ CH₂

C1.010 CF₃ CH₂

C1.011 CF₃ CH₂

C1.012 CF₃ CH₂

C1.013 CF₃ CH₂

C1.014 CF₃ CH₂

C1.015 CF₃ CH₂

C1.016 CF₃ CH₂

C1.017 CF₃ CH₂

C1.018 CF₃ CH₂

C1.019 CF₃ CH₂

C1.020 CF₃ CH₂

C1.021 CF₃ CH₂

C1.022 CF₃ CH₂

C1.023 CF₃ CH₂

TABLE C2 Compounds of formula IAc₂: (IAc₂)

Phys. Comp. No. R₃ L

data C2.001 CF₃ CH₂

C2.002 CF₂H CH₂

C2.003 CF₃ CH₂

C2.004 CF₃ CH₂

C2.005 CF₃ CH₂

C2.006 CF₃ CH₂

C2.007 CF₃ CH₂

C2.008 CF₃ CH₂

C2.009 CF₃ CH₂

C2.010 CF₃ CH₂

C2.011 CF₃ CH₂

C2.011 CF₃ CH₂

C2.012 CF₃ CH₂

C2.013 CF₃ CH₂

C2.014 CF₃ CH₂

C2.015 CF₃ CH₂

C2.016 CF₃ CH₂

C2.017 CF₃ CH₂

C2.018 CF₃ CH₂

C2.019 CF₃ CH₂

C2.020 CF₃ CH₂

C2.021 CF₃ CH₂

C2.022 CF₃ CH₂

C2.023 CF₃ CH₂

TABLE D1 Compounds of formula IAd: (IAd₁)

Phys. Comp. No. R₃ L

data D1.001 CF₃ CH₂

D1.002 CF₂H CH₂

D1.003 CF₃ CH₂

D1.004 CF₃ CH₂

D1.005 CF₃ CH₂

D1.006 CF₃ CH₂

D1.007 CF₃ CH₂

D1.008 CF₃ CH₂

D1.009 CF₃ CH₂

D1.010 CF₃ CH₂

D1.011 CF₃ CH₂

D1.012 CF₃ CH₂

D1.013 CF₃ CH₂

D1.014 CF₃ CH₂

D1.015 CF₃ CH₂

D1.016 CF₃ CH₂

D1.017 CF₃ CH₂

D1.018 CF₃ CH₂

D1.019 CF₃ CH₂

D1.020 CF₃ CH₂

D1.021 CF₃ CH₂

D1.022 CF₃ CH₂

D1.023 CF₃ CH₂

TABLE S1 Compounds of formula II: (IIa)

Comp. No. Y R₃ L

Phys. data S1.001 (P7) OH CF₂Cl CH₂

amorphous crystals S1.002 OC₂H₅ CF₃ CH₂

132-133° C. S1.003 OH CF₃ CH₂

amorphous crystals S1.004 (P4) OH CF₃ CH₂

amorphous crystals S1.005 OC₂H₅ CF₃ CH₂

solid S1.006 OH CF₃ CH₂

solid S1.007 OC₂H₅ CF₃ CH₂

solid S1.008 OH CF₃ CH₂

m.p.: 210° C. S1.009 OC₂H₅ CF₃ CH₂

solid S1.010 OH CF₃ CH₂

m:p.: 145° C. S1.011 OC₂H₅ CF₃ CH₂

solid S1.012 OH CF₃ CH₂

m.p.: 189° C. S1.013 OC₂H₅ CF₃ CH₂

m.p.: 91° C. S1.014 OH CF₃ CH₂

solid S1.015 OC₂H₅ CF₃ CH₂

m.p.: 109° C. S1.016 OH CF₃ CH₂

m.p.: 191° C. S1.017 OC₂H₅ CF₃ CH₂

waxy S1.018 OH CF₃ CH₂

solid S1.019 OC₂H₅ CF₃ CH₂

m.p.: 82° C. S1.020 OH CF₃ CH₂

m.p.: 142° C. S1.021 OC₂H₅ CF₃ CH₂

resin S1.022 OH CF₃ CH₂

solid S1.023 OC₂H₅ CF₃ CH₂

m.p.: 114° C. S1.024 OH CF₃ CH₂

m.p.: 165° C. S1.025 OC₂H₅ CF₃ CH₂

S1.026 OH CF₃ CH₂

m.p.: 128° C. S1.027 OC₂H₅ CF₃ CH₂

m.p.: 123° C. S1.028 OH CF₃ CH₂

m.p.: 166° C. S1.029 OC₂H₅ CF₃ CH₂

m.p.: 116° C. S1.030 OH CF₃ CH₂

m.p.: 174° C. S1.031 OC₂H₅ CF₃ CH₂

solid S1.032 OH CF₃ CH₂

m.p.: 184° C. S1.033 OC₂H₅ CF₃ CH₂

solid S1.034 OH CF₃ CH₂

solid S1.035 OC₂H₅ CF₃ CH₂

solid S1.036 OH CF₃ CH₂

solid S1.037 OC₂H₅ CF₃ CH₂

solid S1.038 OH CF₃ CH₂

solid S1.039 OC₂H₅ CF₃ CH₂

solid S1.040 OH CF₃ CH₂

solid S1.041 OC₂H₅ CF₃ CH₂

solid S1.042 OH CF₃ CH₂

solid S1.043 OC₂H₅ CF₃ CH₂

solid S1.044 OH CF₃ CH₂

solid S1.045 OC₂H₅ CF₃ CH₂

solid S1.046 OH CF₃ CH₂

solid S1.047 (P6) OH CF₃ CH₂

solid S1.048 OH CF₃ CH₂

solid S1.049 OH CF₃ CH₂

crystalline S1.050 OC₂H₅ CClF₂ CH₂

m.p.: 87-88° C. S1.051 OH CClF₂ CH₂

m.p.: 180-182° C. S1.052 OC₂H₅ CClF₂ CH₂

S1.053 OH CClF₂ CH₂

m.p.: 173-174° C. S1.054 OC₂H₅ CCHF₂ CH₂

S1.055 OH CCHF₂ CH₂

S1.056 OC₂H₅ CCHF₂ CH₂

resin S1.057 OH CCHF₂ CH₂

S1.058 OC₂H₅ CCHF₂ CH₂

S1.059 OH CF₃ CH₂

solid S1.060 OH CF₃ CH₂OCH₂CH₂

solid S1.061 OH CF₃ CH₂

solid S1.062 OH CF₃ CH₂

solid S1.063 OH CF₃ CH₂

solid S1.064 OH CClF₂ CH₂

S1.065 OH CClF₂ CH₂

S1.066 OH CClF₂ CH₂

S1.067 OH CClF₂ CH₂

S1.068 OH CHF₂ CH₂

S1.069 OH CHF₂ CH₂

S1.070 OH CHF₂ CH₂

S1.071 OH CHF₂ CH₂

S1.072 OC₂H₅ CF₃ CH₂

m.p.: 122° C. S1.073 OH CF₃ CH₂

m.p.: 182° C. S1.074 OC₂H₅ CF₃ CH₂

m.p.: 132° C. S1.075 OH CF₃ CH₂

m.p.: 255° C. S1.076 OC₂H₅ CF₃ CH₂

m.p.: 113° C. S1.077 OH CF₃ CH₂

m.p.: 228° C. S1.078 (P5) OC₂H₅ CF₃ CH₂

amorphous crystals S1.079 (P7) OC₂H₅ CF₂Cl CH₂

resin

BIOLOGICAL EXAMPLES EXAMPLE B1 Herbicidal Action Prior to Emergence of the Plants (Pre-Emergence Action)

Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastic pots Immediately after sowing, the test compounds, in the form of an aqueous suspension (prepared from a 25% wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from a 25% emulsifiable concentrate (Example F1, c)), are applied by spraying in a concentration corresponding to 125 g or 250 g of active ingredient/ha (500 litres of water/ha). The test plants are then grown in a greenhouse under optimum conditions. After a test duration of 3 weeks, the test is evaluated in accordance with a scale of nine ratings (10=total damage, 0=no action). Ratings of from 10 to 7 (especially from 10 to 8) indicate good to very good herbicidal action. TABLE B1 Pre-emergence action of compounds of formula I: Ex. No. gr. a.i./ha Panicum Echinochloa Cyperus Scirpus Sida Abutilon Amaranthus Chenopodium A1.055 250 9 10 10 9 10 10 0 10 A1.073 250 10 3 10 10 9 10 10 10 A1.079 250 9 5 8 10 10 10 4 8 A1.091 250 4 9 8 9 7 10 8 9 A6.073 250 10 0 7 10 9 10 9 10 A6.079 250 9 7 6 9 6 10 7 10 A6.100 250 10 10 6 10 10 10 10 10 A8.008 250 10 10 0 0 10 10 nt 10 A8.080 250 9 10 0 8 9 10 0 10 B1.008 250 10 9 9 10 9 10 10 10 B1.080 250 10 10 9 9 0 8 0 10 B1.096 250 7 nt 7 7 7 10 10 10 B1.170 250 9 9 8 9 9 9 9 10

EXAMPLE B2 Post-Emergence Herbicidal Action

In a greenhouse, monocotyledonous and dicotyledonous test plants are grown in standard soil in plastic pots and at the 4- to 6-leaf stage are sprayed with an aqueous suspension of the test compounds of formula I prepared from a 25% wettable powder (Example F3, b) according to WO 97/34485) or with an emulsion of the test compounds of formula I prepared from a 25% emulsifiable concentrate (Example F1, c) according to WO 97/34485), in a concentration corresponding to 125 g or 250 g of active ingredient/ha (500 litres of water/ha). The test plants are then grown on in a greenhouse under optimum conditions. After a test duration of about 18 days, the test is evaluated in accordance with a scale of nine ratings (10=total damage, 0=no action). Ratings of from 10 to 7 (especially from 10 to 8) indicate good to very good herbicidal action. The compounds of formula I exhibit a strong herbicidal action in this test. TABLE B2 Post-emergence action of compounds of formula I: Ex. No gr. a.i./ha Echinochloa Euphorbia Xanthium Ipomea Amaranthus Chenopodium Sinapis Stellaria A1.001 125 4 4 8 8 8 9 8 8 A1.007 250 8 4 9 9 9 10 8 7 A1.019 250 8 9 9 9 9 9 8 8 A1.031 250 7 8 9 9 9 10 8 9 A1.037 250 4 8 9 9 9 9 8 8 A1.043 250 7 7 9 9 9 9 6 9 A1.049 250 8 9 9 9 9 8 8 8 A1.073 250 9 9 9 10 10 10 10 10 A1.079 250 7 8 7 8 9 9 9 9 A1.091 250 9 8 9 9 9 10 8 10 A1.109 250 8 10 9 9 9 10 3 5 A1.115 250 7 8 9 7 9 9 3 9 A1.181 250 4 8 8 8 9 8 5 7 A1.202 250 8 9 9 9 9 8 8 7 A6.073 250 9 9 9 10 10 10 10 9 A6.082 250 7 7 7 8 8 9 5 9 A6.091 250 9 8 9 8 8 9 8 9 A6.097 250 7 7 7 7 7 9 8 9 A6.100 250 7 7 7 9 9 10 8 9 A7.008 250 7 7 8 7 5 9 9 9 A7.009 250 7 7 7 7 4 9 8 7 A8.008 250 8 8 9 9 9 8 7 6 A8.062 250 9 9 0 8 9 10 9 5 A8.080 250 9 9 8 10 9 10 10 10 A8.095 250 9 0 8 9 9 5 8 7 A8.174 250 0 7 7 8 8 9 7 7 B1.004 250 8 9 9 8 8 9 10 8 B1.005 250 4 9 6 8 9 9 9 8 B1.008 250 9 8 nt 9 9 10 7 8 B1.039 250 9 9 8 8 6 8 9 9 B1.050 250 4 9 8 7 9 9 9 7 B1.056 250 9 9 0 10 9 8 8 7 B1.062 250 4 9 6 7 9 9 8 8 B1.080 250 9 10 8 10 10 10 10 10 B1.096 250 6 7 8 7 7 10 9 8 B1.158 250 4 7 5 8 7 8 7 7 B1.170 250 9 7 6 0 9 9 9 9 B1.194 250 9 9 9 7 9 9 7 8

In a different test arrangement, the Examples according to Table B3 likewise exhibit good to very good post-emergence action on selected test plants. TABLE B3 Ex. No gr. a.i./ha Amaranthus Solanum Nasturtium Stellaria A1.025 250 9 9 9 9 A1.097 250 9 9 10 9 A1.175 250 7 9 8 7 A1.209 250 7 9 9 7 A1.211 250 9 9 10 7 A1.213 250 9 9 9 9 A1.219 250 9 9 10 10 A1.220 250 9 9 10 10 A1.221 250 9 9 10 9 A1.222 250 9 9 10 9 A1.223 250 8 9 10 9 A1.237 250 9 10 9 7 B1.211 250 9 9 10 8 B1.223 250 8 9 10 10 B1.225 250 8 9 10 10 B1.226 250 8 9 10 9 B1.238 250 9 9 8 7 B1.297 250 9 9 10 9 

1. A compound of formula I

wherein L is either a direct bond, an —O—, —S—, —S(O)—, —SO₂—, —N(R_(5a))—, —SO₂N(R_(5b))—, —N(R_(5b))SO₂—, —C(O)N(R_(5c))- or —N(R_(5c))C(O)— bridge, or a C₁-C₄alkylene, C₂-C₄alkenylene or C₂-C₄alkynylene chain which may be mono- or poly-substituted by R₅ and/or interrupted once or twice by an —O—, —S—, —S(O)—, —SO₂—, N(R_(5d))—, —SO₂N(R_(5e))—, —N(R_(5e))SO₂—, —C(O)N(R_(5f))— and/or —N(R_(5f))C(O)— bridge, and when two such bridges are present those bridges are separated at least by one carbon atom, and W is bonded to L by way of a carbon atom or a —N(R_(5e))SO₂— or —N(R_(5f))C(O)— bridge when the bridge L is bonded to the nitrogen atom of W; W is a 4- to 7-membered, saturated, partially saturated or unsaturated ring system U

which contains a ring element U₁, and may contain from one to four further ring nitrogen atoms, and/or two further ring oxygen atoms, and/or two further ring sulfur atoms and/or one or two further ring elements U₂, and the ring system U may be mono- or poly-substituted at a saturated or unsaturated ring carbon atom and/or at a ring nitrogen atom by a group R₈, and two substituents R₈ together are a further fused-on or spirocyclic 3- to 7-membered ring system which may be unsaturated, partially saturated or fully saturated and may in turn be substituted by one or more groups R_(8a) and/or interrupted once or twice by a ring element —O—, —S—, —N(R_(8b))— and/or —C(═O)—; and U₁ and U₂ are each independently of the other(s) —C(═O)—, —C(═S)—, —C(═NR₆)—, —(N═O)—, —S(═O)— or —SO₂—; R₃ and R₄ are each independently of the other C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy-C₁-C₃alkyl, hydrogen, hydroxy, mercapto, halogen, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkoxy-C₁-C₃alkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, C₁-C₃haloalkylthio, C₁-C₃haloalkylsulfinyl, C₁-C₃haloalkylsulfonyl or C₁-C₃alkylsulfonyloxy; R₅ is halogen, C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, C₁-C₃alkoxy-C₁-C₃alkyl or C₁-C₃alkoxy-C₁-C₃alkoxy; R_(5a), R_(5b) and R_(5e) are independently hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl or C₁-C₃alkoxy-C₁-C₃alkyl; R_(5d) is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₃alkoxy-C₁-C₃alkyl, benzyl, cyano, formyl, C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl, C₁-C₄alkylsulfonyl or phenylsulfonyl, it being possible for the phenyl-containing groups to be substituted by R₇; R_(5c) and R_(5f) are each independently of the other hydrogen or C₁-C₃alkyl; R₆ is C₁-C₆alkyl, hydroxy, C₁-C₆alkoxy, cyano or nitro; R₇ is halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, hydroxy, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano or nitro; each R₈ independently is hydrogen, halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, hydroxy, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₃alkoxy-C₁-C₃alkoxy, mercapto, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆-alkylsulfonyloxy, C₁-C₆haloalkylsulfonyloxy, C₃-C₆alkenylthio, C₃-C₆alkynylthio, amino, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, C₁-C₃alkoxy-C₁-C₃alkyl, formyl, C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl, benzyloxycarbonyl, C₁-C₄alkylthiocarbonyl, carboxy, cyano, carbamoyl, phenyl, benzyl, heteroaryl or heterocyclyl, it being possible for the phenyl, benzyl, heteroaryl and heterocyclyl groups to be mono- or poly-substituted by R_(7a); each R_(7a) independently is halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, hydroxy, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano or nitro; each R_(8a) independently is halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, hydroxy, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, mercapto, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl, cyano or nitro; R_(8b) is hydrogen, C₁-C₃alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₃alkoxy-C₁-C₃alkyl or benzyl, it being possible for the phenyl group to be substituted by R_(7b); R_(7b) is halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, hydroxy, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano or nitro; p is 0 or 1; r is 1,2,3,4, 5 or 6; with the provisos that a) R₈ and R_(8a) as halogen or hydrogenmercapto cannot be bonded to a nitrogen atom, b) U₁ as —C(═O)— or —C(═S)— does not form a tautomeric form with a substituent R_(a) as hydrogen when the radical W is bonded to the pyridyl group by way of a C₁-C₄alkylene, C₂-C₄alkenylene or C₂-C₄alkynylene chain L that is interrupted by —O—, —S—, —S(O)—, —SO₂—, —N(R_(5d))—, —SO₂N(R_(5e))— or —N(R_(5e))SO₂—, c) U₁ as —C(═S)— does not form a tautomeric form with a substituent R_(a) as hydrogen when the radical W is bonded to the pyridyl group by way of a —CH═CH— or —C≡C— bridge L or by way of a C₁-C₄alkylene chain L that is interrupted by —O—, —S—, —S(O)—, —SO₂— or —N(C₁-C₄alkyl)—, d) U₁ as —C(═S)— or —C(═NR₆)— wherein R₆ is C₁-C₆alkyl or C₁-C₆alkoxy does not form a tautomeric form with a substituent R_(a) as hydrogen when the radical W is bonded to the pyridyl group directly or by way of a C₁-C₄alkylene chain L; either Q is a group Q₁

wherein A₁ is C(R₁₁R₁₂) or NR₁₃; A₂ is C(R₁₄R₁₅)_(m), C(O), oxygen, NR₁₆ or S(O)_(q); A₃ is C(R₁₇R₁₈) or NR₁₉; with the proviso that A₂ is other than S(O)_(q) when A₁ is NR₁₃ and/or A₃ is NR₁₉; X₁ is hydroxy, O⁻M⁺, wherein M⁺ is a metal cation or an ammonium cation; halogen or S(O)_(n)R₉, wherein m is 1 or 2; q, n and k are each independently of the others 0, 1 or 2; R₉ is C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₂-C₁₂alkynyl, C₃-C₁₂allenyl, C₃-C₁₂cycloalkyl, C₅-C₁₂cycloalkenyl, R₁₀—C₁-C₁₂alkylene or R₁₀—C₂-C₁₂alkenylene, wherein the alkylene or alkenylene chain may be interrupted by —O—, —S(O)_(k)— and/or —C(O)— and/or mono- to penta-substituted by R₂₀; or phenyl, which may be mono- to penta-substituted by R_(7c); R_(7c) is halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, hydroxy, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano or nitro; R₁₀ is halogen, cyano, rhodano, hydroxy, C₁-C₆alkoxy, C₂-C₆alkenyloxy, C₂-C₆alkynyloxy, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₂-C₆alkenylthio, C₂-C₆alkynylthio, C₁-C₆alkylsulfonyloxy, phenylsulfonyloxy, C₁-C₆alkylcarbonyloxy, benzoyloxy, C₁-C₄alkoxy-carbonyloxy, C₁-C₆alkylcarbonyl, C₁-C₄alkoxycarbonyl, benzoyl, aminocarbonyl, C₁-C₄alkyl-aminocarbonyl, C₃-C₆cycloalkyl, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl; it being possible for the phenyl-containing groups in turn to be substituted by R_(7d); R_(7d) is halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, hydroxy, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano or nitro; R₂₀ is hydroxy, halogen, C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, cyano, carbamoyl, carboxy, C₁-C₄alkoxycarbonyl or phenyl; it being possible for phenyl to be substituted by R_(7e); R_(7e) is halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, hydroxy, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano or nitro; R₁₁ and R₁₇ are each independently of the other hydrogen, C₁-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkoxycarbonyl, hydroxy, C₁-C₄alkoxy, C₃-C₄alkenyloxy, C₃-C₄alkynyloxy, hydroxy-C₁-C₄alkyl, C₁-C₄alkylsulfonyloxy-C₁-C₄alkyl, halogen, cyano or nitro; or, when A₂ is C(R₁₄R₁₅)_(m), R₁₇ together with R₁₁ forms a direct bond or a C₁-C₃alkylene bridge; R₁₂ and R₁₈ are each independently of the other hydrogen, C₁-C₄alkyl or C₁-C₄alkylthio, C₁-C₄alkylsulfinyl or C₁-C₄alkylsulfonyl; or R₁₂ together with R₁₁, and/or R₁₈ together with R₁₇ form a C₂-C₅alkylene chain which may be interrupted by —O—, —C(O)—, —O— and —C(O)— or —S(O)_(t)—; R₁₃ and R_(1g) are each independently of the other hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₄alkenyl, C₃-C₄alkynyl or C₁-C₄alkoxy; R₁₄ is hydrogen, hydroxy, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃hydroxyalkyl, C₁-C₄alkoxy-C₁-C₃-alkyl, C₁-C₄alkylthio-C₁-C₃alkyl, C₁-C₄alkylcarbonyloxy-C₁-C₃alkyl, C₁-C₄alkylsulfonyloxy-C₁-C₃alkyl, tosyloxy-C₁-C₃alkyl, di(C₁-C₄alkoxy)-C₁-C₃alkyl, C₁-C₄alkoxycarbonyl, C₃-C₅-oxacycloalkyl, C₃-C₅thiacycloalkyl, C₃-C₄dioxacycloalkyl, C₃-C₄dithiacycloalkyl, C₃-C₄oxathiacycloalkyl, formyl, C₁-C₄alkoxyiminomethyl, carbamoyl, C₁-C₄alkylaminocarbonyl or di-(C₁-C₄alkyl)aminocarbonyl; or R₁₄ together with R₁₁, R₁₂, R₁₃, R₁₅, R₁₇, R₁₈ or R₁₉ or, when m is 2, also together with R₁₄ forms a direct bond or a C₁-C₄alkylene bridge; R₁₅ is hydrogen, C₁-C₃alkyl or C₁-C₃haloalkyl; R₁₆ is hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₄alkoxycarbonyl, C₁-C₄alkylcarbonyl or N,N-di(C₁-C₄alkyl)aminocarbonyl; or Q is a group Q₂

wherein R₂₁ and R₂ are hydrogen or C₁-C₄alkyl; X₂ is hydroxy, O⁻M⁺, wherein M⁺ is an alkali metal cation or ammonium cation; halogen, C₁-C₁₂alkylsulfonyloxy, C₁-C₁₂alkylthio, C₁-C₁₂alkylsulfinyl, C₁-C₁₂alkylsulfonyl, C₁-C₁₂haloalkylthio, C₁-C₁₂haloalkylsulfinyl, C₁-C₁₂haloalkylsulfonyl, C₁-C₆alkoxy-C₁-C₆alkylthio, C₁-C₆alkoxy-C₁-C₆alkylsulfinyl, C₁-C₆alkoxy-C₁-C₆alkylsulfonyl, C₃-C₁₂alkenylthio, C₃-C₁₂alkenylsulfinyl, C₃-C₁₂alkenylsulfonyl, C₃-C₁₂alkynylthio, C₃-C₁₂alkynylsulfinyl, C₃-C₁₂alkynylsulfonyl, C₁-C₄alkoxycarbonyl-C₁-C₄alkylthio, C₁-C₄alkoxycarbonyl-C₁-C₄alkylsulfinyl, C₁-C₄alkoxycarbonyl-C₁-C₄alkylsulfonyl, benzyloxy or phenylcarbonylmethoxy; it being possible for the phenyl-containing groups to be substituted by R_(7f); R_(7f) is halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, hydroxy, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano or nitro; or Q is a group Q₃

wherein R₃₁ is C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl or halo-substituted C₃-C₆cycloalkyl; R₃₂ is hydrogen, C₁-C₄alkoxycarbonyl, carboxy or a group S(O)_(S)R₃₃; R₃₃ is C₁-C₆alkyl or C₁-C₃alkylene, which may be substituted by halogen, C₁-C₃alkoxy, C₂-C₃alkenyl or by C₂-C₃alkynyl; and s is 0, 1 or 2; or Q is a group Q₄

wherein R₄, is C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl or halo-substituted C₃-C₆cycloalkyl; or an agrochemically acceptable salt or any stereoisomer or tautomer of a compound of formula I.
 2. A compound of formula II

wherein Y is chlorine, cyano, hydroxy, C₁-C₄alkoxy, benzyloxy, phenoxy, allyloxy, a group

or a group Q₀, wherein Q₀ is accordingly a group Q linked to oxygen and Q, L, U₁, R₁, R₂, R₃, R₄, R₃₁, R₃₂, R₃₃ and p are as defined for formula I in claim
 1. 3. A herbicidal and plant-growth-inhibiting composition, which comprises a herbicidally effective amount of a compound of formula I, according to claim 1, on an inert carrier.
 4. A method of controlling undesired plant growth, which comprises applying a herbicidally effective amount of a compound of formula I, according to claim 1, or of a composition comprising such a compound, to the plants or to the locus thereof.
 5. A method of inhibiting plant growth, which comprises applying a herbicidally effective amount of a compound of formula I, according to claim 1, or of a composition comprising such a compound, to the plants or to the locus thereof. 